Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B22—CASTING; POWDER METALLURGY
  • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
  • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
  • B22F1/17—Metallic particles coated with metal
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B22—CASTING; POWDER METALLURGY
  • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
  • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B22—CASTING; POWDER METALLURGY
  • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
  • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
  • B22F1/05—Metallic powder characterised by the size or surface area of the particles
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B22—CASTING; POWDER METALLURGY
  • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
  • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
  • B22F1/06—Metallic powder characterised by the shape of the particles
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B22—CASTING; POWDER METALLURGY
  • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
  • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
  • B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
  • B22F1/103—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material containing an organic binding agent comprising a mixture of, or obtained by reaction of, two or more components other than a solvent or a lubricating agent
• • 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
  • B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
  • B22F7/06—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite workpieces or articles from parts, e.g. to form tipped tools
  • B22F7/062—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite workpieces or articles from parts, e.g. to form tipped tools involving the connection or repairing of preformed parts
  • B22F7/064—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite workpieces or articles from parts, e.g. to form tipped tools involving the connection or repairing of preformed parts using an intermediate powder layer
• • 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
  • B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
  • B22F7/06—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite workpieces or articles from parts, e.g. to form tipped tools
  • B22F7/08—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite workpieces or articles from parts, e.g. to form tipped tools with one or more parts not made from powder
• • 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
  • B22F9/02—Making metallic powder or suspensions thereof using physical processes
  • B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
  • B22F9/08—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying
• • 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
• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22C—ALLOYS
  • C22C1/00—Making non-ferrous alloys
  • C22C1/04—Making non-ferrous alloys by powder metallurgy
  • C22C1/0466—Alloys based on noble metals
• • 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
  • H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
  • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
  • H01B1/20—Conductive material dispersed in non-conductive organic material
  • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
  • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
  • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W40/00—Arrangements for thermal protection or thermal control
  • H10W40/60—Securing means for detachable heating or cooling arrangements, e.g. clamps
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W72/00—Interconnections or connectors in packages
  • H10W72/30—Die-attach connectors
• • 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
  • B22F9/02—Making metallic powder or suspensions thereof using physical processes
  • B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
  • B22F9/08—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying
  • B22F9/082—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying atomising using a fluid
  • B22F2009/0832—Handling of atomising fluid, e.g. heating, cooling, cleaning, recirculating
• • 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
  • B22F2301/00—Metallic composition of the powder or its coating
  • B22F2301/25—Noble metals, i.e. Ag Au, Ir, Os, Pd, Pt, Rh, Ru
  • B22F2301/255—Silver or gold
• • 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
  • B22F2304/00—Physical aspects of the powder
  • B22F2304/05—Submicron size particles
  • B22F2304/054—Particle size between 1 and 100 nm
• • 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
  • B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy
• • 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
  • B23K35/24—Selection of soldering or welding materials proper
  • B23K35/30—Selection of soldering or welding materials proper with the principal constituent melting at less than 1550°C
  • B23K35/3006—Ag as the principal constituent
• • 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
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W40/00—Arrangements for thermal protection or thermal control
  • H10W40/20—Arrangements for cooling
  • H10W40/25—Arrangements for cooling characterised by their materials
  • H10W40/257—Arrangements for cooling characterised by their materials having a heterogeneous or anisotropic structure, e.g. powder or fibres in a matrix, wire mesh or porous structures
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W40/00—Arrangements for thermal protection or thermal control
  • H10W40/70—Fillings or auxiliary members in containers or in encapsulations for thermal protection or control
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W72/00—Interconnections or connectors in packages
  • H10W72/071—Connecting or disconnecting
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W72/00—Interconnections or connectors in packages
  • H10W72/30—Die-attach connectors
  • H10W72/321—Structures or relative sizes of die-attach connectors
  • H10W72/325—Die-attach connectors having a filler embedded in a matrix
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W72/00—Interconnections or connectors in packages
  • H10W72/30—Die-attach connectors
  • H10W72/351—Materials of die-attach connectors
  • H10W72/352—Materials of die-attach connectors comprising metals or metalloids, e.g. solders
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W72/00—Interconnections or connectors in packages
  • H10W72/30—Die-attach connectors
  • H10W72/351—Materials of die-attach connectors
  • H10W72/353—Materials of die-attach connectors not comprising solid metals or solid metalloids, e.g. ceramics
  • H10W72/354—Materials of die-attach connectors not comprising solid metals or solid metalloids, e.g. ceramics comprising polymers
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W90/00—Package configurations
  • H10W90/701—Package configurations characterised by the relative positions of pads or connectors relative to package parts
  • H10W90/731—Package configurations characterised by the relative positions of pads or connectors relative to package parts of die-attach connectors
  • H10W90/734—Package configurations characterised by the relative positions of pads or connectors relative to package parts of die-attach connectors between a chip and a stacked insulating package substrate, interposer or RDL
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W90/00—Package configurations
  • H10W90/701—Package configurations characterised by the relative positions of pads or connectors relative to package parts
  • H10W90/731—Package configurations characterised by the relative positions of pads or connectors relative to package parts of die-attach connectors
  • H10W90/736—Package configurations characterised by the relative positions of pads or connectors relative to package parts of die-attach connectors between a chip and a stacked lead frame, conducting package substrate or heat sink
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/12—All metal or with adjacent metals
  • Y10T428/12181—Composite powder [e.g., coated, etc.]

Definitions

• the present disclosure relates to silver particles, a method for producing silver particles, a paste composition, a semiconductor device, and electrical / electronic parts.
• Patent Document 1 proposes a silver sintered paste using silver nanoparticles that exhibit excellent conductivity by low-temperature firing.
• the disclosure of the present application relates to the following.
• a method for producing silver particles which comprises (A) a step of further forming a silver layer on the surface of silver powder by a liquid phase reduction method.
• (meth) acrylate means acrylate and / or methacrylate.
• the silver particles of the present embodiment have a silver powder and a silver layer composed of primary particles smaller than the silver powder.
• the silver powder constituting the base of the silver particles is not particularly limited, and for example, an atomizing method, an electrolysis method, a chemical reduction method, a crushing method / crushing method, a plasma rotating electrode method, a uniform droplet spraying method, a heat treatment method and the like are known.
• the one prepared by the above method can be used.
• the silver powder may be prepared by an atomizing method, an electrolytic method, or a chemical reduction method from the viewpoint of controlling the particle size and the particle shape.
• the silver powder may have an average particle size of 0.5 ⁇ m or more and 30 ⁇ m or less, may be larger than 0.5 ⁇ m and 20 ⁇ m or less, or may be 1 ⁇ m or more and 20 ⁇ m or less.
• the shape is not particularly limited, and examples thereof include a spherical shape, a plate type, a flake shape, a scale shape, a dendritic shape, a rod shape, a wire shape, and an indefinite shape.
• the average particle size of the silver powder is a particle size (50% particle size D50) at which the integrated volume is 50% in the particle size distribution measured by using a laser diffraction type particle size distribution measuring device or the like.
• the silver layer is formed, for example, by reducing a silver compound with a reducing compound and aggregating the primary silver particles liberated from the silver compound.
• the silver compound may be at least one selected from silver nitrate, silver chloride, silver acetate, silver oxalate, and silver oxide, and may be silver nitrate and silver acetate from the viewpoint of solubility in water. ..
• the reducing compound is not particularly limited as long as it has a reducing power for reducing the silver compound and precipitating silver.
• the reducing compound include hydrazine derivatives.
• the hydrazine derivative include hydrazine monohydrate, methylhydrazine, ethylhydrazine, n-propylhydrazine, i-propylhydrazine, n-butylhydrazine, i-butylhydrazine, sec-butylhydrazine, t-butylhydrazine, n.
• -Pentyl hydrazine i-Pentyl hydrazine, neo-Pentyl hydrazine, t-Pentyl hydrazine, n-hexyl hydrazine, i-hexyl hydrazine, n-heptyl hydrazine, n-octyl hydrazine, n-nonyl hydrazine, n-decyl hydrazine, n -Undecyl hydrazine, n-dodecyl hydrazine, cyclohexyl hydrazine, phenyl hydrazine, 4-methylphenyl hydrazine, benzyl hydrazine, 2-phenylethyl hydrazine, 2-hydrazine ethanol, acetohydrazine and the like can be mentioned. These may be used alone or in combination of two or more.
• the average particle size of the primary particles may be 10 to 100 nm, 10 to 50 nm, or 20 to 50 nm.
• the average particle size of the primary particles was measured by observing the cross section of spherical silver particles cut with a focused ion beam (FIB) device with a field emission scanning electron microscope (FE-SEM). It can be obtained by averaging the number of particle sizes. Specifically, it can be measured by the method described in Examples.
• FIB focused ion beam
• FE-SEM field emission scanning electron microscope
• the average particle size of the silver particles may be 0.5 to 5.0 ⁇ m, 0.5 to 3.0 ⁇ m, or 1.0 to 3.0 ⁇ m. When the average particle size of the silver particles is 0.5 ⁇ m or more, the storage stability is good, and when it is 5.0 ⁇ m or less, the sinterability is good.
• the average particle size of the silver particles is a particle size (50% particle size D50) at which the integrated volume is 50% in the particle size distribution measured using a laser diffraction type particle size distribution measuring device. It can be measured by the method described in the example.
• the tap density of the silver particles may be 4.0 to 7.0 g / cm 3 , 4.5 to 7.0 g / cm 3 , and 4.5 to 6.5 g / cm 3. It may be.
• the tap density of the silver particles is 4.0 g / cm 3 or more, the silver particles can be highly filled in the paste, and when the tap density is 7.0 g / cm 3 or less, the precipitation of the silver particles in the paste is reduced. can do.
• the tap density of the silver particles can be measured using a tap density measuring device, and specifically, can be measured by the method described in Examples.
• the specific surface area of the silver particles determined by the BET method may be 0.5 to 1.5 m 2 / g, 0.5 to 1.2 m 2 / g, or 0.6 to 1 .2 m 2 / g may be used.
• the specific surface area of the silver particles is 0.5 m 2 / g or more, the contact between the silver particles can be increased, and when the specific surface area is 1.5 m 2 / g or less, the viscosity of the paste can be reduced.
• the specific surface area of the silver particles can be measured by the BET one-point method by nitrogen adsorption using a specific surface area measuring device, and specifically, can be measured by the method described in Examples.
• the method for producing silver particles of the present embodiment includes (A) a step of further forming a silver layer on the surface of silver powder (hereinafter, also simply referred to as a silver layer forming step) by a liquid phase reduction method.
• a silver layer forming step In the silver layer forming step, (A) silver powder, (B) silver compound, and (C) reducing compound are mixed in the liquid phase.
• (A) silver powder As the (A) silver powder, (B) silver compound, and (C) reducing compound, those described in the above section ⁇ Silver particles> can be used.
• the silver compound (B) may be used as a silver ammine complex solution from the viewpoint of complex stability.
• the silver ammine complex solution is not particularly limited. Generally, it is obtained by dissolving the silver compound in aqueous ammonia (see, for example, Japanese Patent Application Laid-Open No. 2014-181399), but it may be prepared by adding an amine compound to the silver compound and then dissolving it in alcohol.
• the amount of ammonia added may be 2 to 50 mol, 5 to 50 mol, or 10 to 50 mol per 1 mol of silver in the aqueous solution containing the (B) silver compound.
• the average particle size of the primary silver particles liberated from the silver compound can be within the above range.
• the silver ammine complex in the silver ammine complex solution is reduced with the (C) reducing compound to obtain a silver particle-containing slurry.
• the silver ammine complex in the silver ammine complex solution is reduced with the (C) reducing compound to obtain a silver particle-containing slurry.
• silver is liberated from the silver ammine complex, and (A) secondary particles in which the primary particles of silver are aggregated are formed around the silver powder. Silver particles are formed.
• the aggregation of the primary particles can be controlled and obtained.
• the average particle size of the secondary particles (silver particles) can be within the above range.
• the content of the reducing compound (C) may be 0.25 to 20 mol, 0.25 to 10 mol, or 1.0 to 5.0 mol per 1 mol of silver in the silver ammine complex. You may.
• the temperature of the silver ammine complex solution when reducing the silver ammine complex may be less than 30 ° C., or may be 0 to 20 ° C.
• the aggregation of the primary particles can be controlled, and the average particle size of the obtained secondary particles can be within the above range.
• an organic protective compound By further adding (D) an organic protective compound to the silver particle-containing slurry obtained as described above, a protecting group can be introduced into the silver particles in the silver particle-containing slurry.
• the (D) organic protective compound include carboxylic acids, alkylamines, carboxylic acid amine salts, and amides.
• the organic protective compound (D) may be at least one selected from a carboxylic acid, an alkylamine, and a carboxylic acid amine salt from the viewpoint of particle stability, and is a carboxylic acid from the viewpoint of enhancing dispersibility. You may.
• carboxylic acid examples include monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, capric acid, octyl acid, nonanoic acid, capric acid, oleic acid, stearic acid and isostearic acid; , Malonic acid, succinic acid, glutaric acid, adipic acid, pimelli acid, suberic acid, azelaic acid, sebacic acid, diglycolic acid and other dicarboxylic acids; benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, salicylic acid, gallic acid, etc.
• monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, capric acid, octyl acid, nonanoic acid, capric acid, oleic acid, stearic acid
• Aromatic carboxylic acids examples thereof include glycolic acid, lactic acid, tartronic acid, malic acid, glyceric acid, hydroxybutyric acid, tartrate acid, citric acid, hydroxy acid such as isocitrate. These may be used alone or in combination of two or more.
• the blending amount of the (D) organic protective compound may be 1 to 20 mmol, 1 to 10 mmol, or 1 to 5 mmol with respect to 1 mol of the silver particles.
• the blending amount of the organic protective compound is 1 mmol or more, the silver particles can be dispersed in the resin, and when it is 20 mmol or less, the silver particles can be dispersed in the resin without impairing the sinterability.
• the silver particles obtained by the method for producing silver particles of the present embodiment are secondary particles in which nano-sized silver primary particles are aggregated on the surface of the silver powder, so that the surface of the silver primary particles has high activity. It is maintained and has the separability (self-sinterability) between secondary particles at low temperature. Further, the sintering of the silver particles and the sintering of the silver particles and the joining member proceed in parallel. Therefore, by using the silver particles, a paste composition having excellent thermal conductivity and adhesive properties can be obtained.
• the paste composition of this embodiment contains the above-mentioned silver particles. Therefore, the paste composition of the present embodiment has a low viscosity and good dispersibility, and can obtain a cured product having excellent adhesive properties and thermal conductivity, small volume shrinkage, and excellent low stress properties.
• the paste composition of the present embodiment can be used as a die-attaching material for element bonding, a heat-dissipating member bonding material, and the like.
• the paste composition of the present embodiment can be an adhesive material (paste) having an appropriate viscosity by containing a thermosetting resin.
• the thermosetting resin can be used without particular limitation as long as it is a thermosetting resin generally used for adhesives.
• the thermosetting resin may be a liquid resin or a resin that is liquid at room temperature (25 ° C.).
• the thermosetting resin may be at least one selected from cyanate resin, epoxy resin, acrylic resin and maleimide resin. These may be used alone or in combination of two or more.
• the cyanate resin is a compound having an -NCO group in the molecule, and is a resin that is cured by forming a three-dimensional network structure by reacting the -NCO group by heating.
• Specific examples of the cyanate resin include 1,3-disyanatobenzene, 1,4-disyanatobenzene, 1,3,5-trisianatobenzene, 1,3-disyanatonaphthalene, and 1,4-disianato.
• a prepolymer having a triazine ring formed by trimerizing the cyanate group of these polyfunctional cyanate resins can also be used.
• the prepolymer is obtained by polymerizing the above-mentioned polyfunctional cyanate resin monomer using, for example, an acid such as mineral acid or Lewis acid, a base such as sodium alcoholate or tertiary amines, or a salt such as sodium carbonate as a catalyst. Be done.
• the curing accelerator for the cyanate resin generally known ones can be used.
• organic metal complexes such as zinc octylate, tin octylate, cobalt naphthenate, zinc naphthenate, iron acetylacetone; metal salts such as aluminum chloride, tin chloride and zinc chloride; amines such as triethylamine and dimethylbenzylamine.
• metal salts such as aluminum chloride, tin chloride and zinc chloride
• amines such as triethylamine and dimethylbenzylamine.
• Epoxy resin is a compound having one or more glycidyl groups in the molecule, and is a resin that forms a three-dimensional network structure and is cured by reacting the glycidyl groups by heating.
• the epoxy resin may be a compound containing two or more glycidyl groups in one molecule. This is because a compound having only one glycidyl group cannot exhibit sufficient cured product properties even if it is reacted.
• a compound containing two or more glycidyl groups in one molecule can be obtained by epoxidizing a compound having two or more hydroxyl groups.
• Such compounds include bisphenol compounds such as bisphenol A, bisphenol F, and biphenol or derivatives thereof, hydrogenated bisphenol A, hydrogenated bisphenol F, hydrogenated biphenol, cyclohexanediol, cyclohexanedimethanol, and alicyclic such as cyclohexanediethanol.
• Bifunctional diols having a structure or derivatives thereof, butane diols, hexane diols, octane diols, nonane diols, decane diols and other aliphatic diols or derivatives thereof epoxidized; trihydroxyphenylmethane skeleton, aminophenol Trifunctional ones obtained by epoxidizing compounds having a skeleton; polyfunctional ones obtained by epoxidizing phenol novolac resin, cresol novolac resin, phenol aralkyl resin, biphenyl aralkyl resin, naphthol aralkyl resin, etc. Not limited.
• the epoxy resin is formed into a paste at room temperature (25 ° C.) as a paste composition, it may be liquid alone or as a mixture at room temperature (25 ° C.). It is also possible to use reactive diluents as is normally done. Examples of the reactive diluent include monofunctional aromatic glycidyl ethers such as phenylglycidyl ether and cresyl glycidyl ether, and aliphatic glycidyl ethers.
• Examples of the curing agent for the epoxy resin include aliphatic amines, aromatic amines, dicyandiamides, dihydrazide compounds, acid anhydrides, and phenol resins.
• Examples of the dihydrazide compound include carboxylic acid dihydrazides such as adipic acid dihydrazide, dodecanoic acid dihydrazide, isophthalic acid dihydrazide, and p-oxybenzoic acid dihydrazide.
• Acid anhydrides include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, dodecenyl succinic anhydride, maleic anhydride and polybutadiene reactants, and maleic anhydride and styrene. Examples include polymers.
• a curing accelerator can be added to promote curing.
• the curing accelerator for the epoxy resin include imidazoles, triphenylphosphine or tetraphenylphosphine and salts thereof, amine compounds such as diazabicycloundecene and salts thereof.
• the curing accelerator includes, for example, 2-methylimidazole, 2-ethylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-.
• 2-C 11 H 23 - imidazole may be imidazol compounds such as the adduct of 2-methylimidazole and 2,4-diamino-6-vinyl-triazine, melting point 180 ° C.
• the above imidazole compound may be used.
• acrylic resin examples include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 3-hydroxybutyl (meth).
• Examples thereof include (meth) acrylate having a carboxy group obtained by reacting (meth) acrylate with dicarboxylic acid or a derivative thereof.
• dicarboxylic acids that can be used here include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, phthalic acid, and tetrahydrophthalic acid. , Hexahydrophthalic acid and derivatives thereof and the like.
• acrylic resin a compound having a (meth) acrylic group in a polyether, polyester, polycarbonate, or poly (meth) acrylate having a molecular weight of 100 to 10,000; a (meth) acrylate having a hydroxyl group; having a hydroxyl group.
• examples include (meth) acrylamide.
• Maleimide resin is a compound containing one or more maleimide groups in one molecule, and is a resin that forms a three-dimensional network structure and cures when the maleimide groups react with each other by heating.
• the maleimide resin include N, N'-(4,4'-diphenylmethane) bismaleimide, bis (3-ethyl-5-methyl-4-maleimidephenyl) methane, and 2,2-bis [4- (4). -Maleimidephenoxy) Phenyl]
• Examples of bismaleimide resins such as propane.
• the maleimide resin may be a compound obtained by reacting diamine dimerate with maleic anhydride; a compound obtained by reacting a maleimided amino acid such as maleimide acetic acid or maleimide caproic acid with a polyol.
• the maleimided amino acid can be obtained by reacting maleic anhydride with aminoacetic acid or aminocaproic acid.
• the polyol may be a polyether polyol, a polyester polyol, a polycarbonate polyol, a poly (meth) acrylate polyol, or one that does not contain an aromatic ring.
• the content of the thermosetting resin may be 1 to 20 parts by mass or 5 to 18 parts by mass with respect to 100 parts by mass of the silver particles.
• the thermosetting resin is 1 part by mass or more, sufficient adhesiveness can be obtained by the thermosetting resin, and when the thermosetting resin is 20 parts by mass or less, the ratio of the silver component is controlled to decrease. , High thermal conductivity can be sufficiently ensured, and heat dissipation can be improved.
• the amount of organic components does not increase too much, deterioration due to light and heat is suppressed, and as a result, the life of the light emitting device can be extended.
• the paste composition of the present embodiment may further contain a diluent from the viewpoint of workability.
• a diluent examples include butyl carbitol, cellosolve acetate, ethyl cellosolve, butyl cellosolve, butyl cellosolve acetate, butyl carbitol acetate, diethylene glycol dimethyl ether, diacetone alcohol, N-methyl-2-pyrrolidone (NMP), dimethylformamide, N, Examples thereof include N-dimethylacetamide (DMAc), ⁇ -butyrolactone, 1,3-dimethyl-2-imidazolidinone, 3,5-dimethyl-1-adamantanamine (DMA) and the like. These may be used alone or in combination of two or more.
• the content thereof may be 3 to 20 parts by mass or 4 to 15 parts by mass with respect to 100 parts by mass of silver particles. It may be 4 to 10 parts by mass.
• the content of the diluent is 3 parts by mass or more, the viscosity can be reduced by dilution, and when it is 20 parts by mass or less, the generation of voids when curing the paste composition of the present embodiment is controlled. ..
• the paste composition of the present embodiment is generally blended in this type of composition as a curing accelerator; a low stress agent such as rubber or silicone; a coupling agent; a defoaming agent; a surfactant.
• Activators; colorants such as pigments and dyes; polymerization initiators; various polymerization inhibitors; antioxidants; solvents; various other additives can be contained as required.
• One of these additives may be used alone, or two or more thereof may be mixed and used.
• the paste composition of the present embodiment is prepared by sufficiently mixing the above-mentioned silver particles, a thermosetting resin contained as necessary, a diluent and various additives, and then using a disperser, a kneader, a three-roll mill or the like. It can be prepared by performing a kneading treatment and then defoaming.
• the thermal conductivity of the cured product of the paste composition of the present embodiment may be 35 W / m ⁇ K or more, or 40 W / m ⁇ K or more.
• the thermal conductivity can be measured by the method described in Examples.
• the viscosity of the paste composition of the present embodiment may be 70 to 200 Pa ⁇ s or 100 to 200 Pa ⁇ s.
• the above viscosity is a value measured at 25 ° C. using an E-type viscometer (3 ° cone). Specifically, it can be measured by the method described in Examples.
• the semiconductor device of the present embodiment is formed by adhering a semiconductor element onto a substrate serving as an element support member by using the above-mentioned paste composition. That is, here, the paste composition is used as a die attach material, and the semiconductor element and the substrate are adhered and fixed via the die attach material.
• the semiconductor element may be any known semiconductor element, and examples thereof include a transistor and a diode. Further, examples of the semiconductor element include a light emitting element such as an LED.
• the type of light emitting element is not particularly limited, and examples thereof include those in which a nitride semiconductor such as InN, AlN, GaN, InGaN, AlGaN, and InGaAlN is formed as a light emitting layer on a substrate by the MOBVC method or the like. Be done.
• the element support member include a support member made of a material such as copper, copper-plated copper, PPF (preplating lead frame), glass epoxy, and ceramics.
• the semiconductor element can be bonded to a base material that has not been metal-plated.
• the semiconductor device thus obtained has a dramatically improved connection reliability with respect to the temperature cycle after mounting as compared with the conventional one. Further, since the electric resistance value is sufficiently small and the change with time is small, there is an advantage that the output does not decrease with time even when driven for a long time and has a long life.
• the electric / electronic component of the present embodiment is formed by adhering a heat radiating member to a heat generating member by using the above-mentioned paste composition. That is, here, the paste composition is used as a material for adhering the heat radiating member, and the heat radiating member and the heat generating member are adhered and fixed via the paste composition.
• the heat generating member may be the above-mentioned semiconductor element or a member having the semiconductor element, or may be another heat generating member.
• Examples of the heat generating member other than the semiconductor element include an optical pickup and a power transistor.
• examples of the heat radiating member include a heat sink and a heat spreader.
• the heat generated by the heat radiating member can be efficiently discharged to the outside by the heat radiating member, and the temperature of the heat generating member rises. Can be suppressed.
• the heat generating member and the heat radiating member may be directly bonded to each other via a heat radiating member bonding material, or may be indirectly bonded by sandwiching another member having high thermal conductivity.
• the average particle size of the silver primary particles forming the silver layer is 20 nm
• the average particle size of the secondary particles in which the primary particles are aggregated is 1.9 ⁇ m
• the tap density of the obtained silver particles 1 is 5.
• the specific surface area was 1.0 m 2 / g and 7 g / cm 3.
• the liquid temperature was set to 10 ° C., and 28 mL of a 20 mass% hydrazine monohydrate aqueous solution (manufactured by Hayashi Junyaku Kogyo Co., Ltd.) was added dropwise over 60 seconds while stirring to precipitate silver on the surface of silver powder. A particle-containing slurry was obtained. To this slurry, 1% by mass of oleic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) was added with respect to the amount of silver, and the mixture was stirred for 10 minutes. The slurry was filtered, the filter medium was washed with water, washed with methanol, and dried at 60 ° C. for 24 hours in a vacuum atmosphere to obtain silver particles 2.
• a 20 mass% hydrazine monohydrate aqueous solution manufactured by Hayashi Junyaku Kogyo Co., Ltd.
• the liquid temperature was set to 10 ° C., and 28 mL of a 20 mass% hydrazine monohydrate aqueous solution (manufactured by Hayashi Junyaku Kogyo Co., Ltd.) was added dropwise over 60 seconds while stirring to precipitate silver on the surface of silver powder. A particle-containing slurry was obtained. To this slurry, 1% by mass of oleic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) was added with respect to the amount of silver, and the mixture was stirred for 10 minutes. The slurry was filtered, the filter medium was washed with water, washed with methanol, and dried at 60 ° C. for 24 hours in a vacuum atmosphere to obtain silver particles 3.
• a 20 mass% hydrazine monohydrate aqueous solution manufactured by Hayashi Junyaku Kogyo Co., Ltd.
• the liquid temperature was set to 10 ° C., and 20 mL of a 20 mass% hydrazine monohydrate aqueous solution (manufactured by Hayashi Junyaku Kogyo Co., Ltd.) was added dropwise over 60 seconds while stirring to precipitate silver on the surface of silver powder. A particle-containing slurry was obtained. To this slurry, 1% by mass of oleic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) was added with respect to the amount of silver, and the mixture was stirred for 10 minutes. The slurry was filtered, the filter medium was washed with water, washed with methanol, and dried at 60 ° C. for 24 hours in a vacuum atmosphere to obtain silver particles 4.
• a 20 mass% hydrazine monohydrate aqueous solution manufactured by Hayashi Junyaku Kogyo Co., Ltd.
• the silver particles 1 to 4 obtained in Synthesis Examples 1 to 4 were evaluated by the following method. The results are shown in Table 1.
• the average particle size of the primary particles is the field emission scanning electron microscope (FE-SEM) (manufactured by JEOL), which is a cross section of spherical silver particles cut with a focused ion beam (FIB) device (JEM-9310FIB manufactured by JEOL). It was determined by averaging the particle diameters of 200 silver particles measured by observing with JSM-6700F).
• FE-SEM field emission scanning electron microscope
• the average particle size of the secondary particles is the particle size (50) at which the integrated volume is 50% in the particle size distribution measured using a laser diffraction type particle size distribution measuring device (manufactured by Shimadzu Corporation, trade name: SALAD-7500 nano). % Particle size D50).
• the tap density was measured as the mass per unit volume (unit: g / cm 3 ) of the silver particles in the vibrated container with a tap density measuring device (Tap-Pak Volumeter, manufactured by Thermo Scientific). ..
• the specific surface area was degassed at 60 ° C. for 10 minutes and then measured by the BET one-point method by nitrogen adsorption using a specific surface area measuring device (Monosorb, manufactured by Quanta Chrome).
• Examples 1 to 9, Comparative Examples 1 to 4 Each component was mixed according to the formulation shown in Table 2 and kneaded with a 3-roll mill to obtain a paste composition. The obtained paste composition was evaluated by the method described below. The results are shown in Table 2. In Table 2, blanks indicate no compounding. The materials shown in Table 2 used in Examples and Comparative Examples are as follows.
• [Silver particle X] (Silver particle 1): Silver particles obtained in Synthesis Example 1 (average particle size of primary particles: 20 nm, average particle size of secondary particles: 1.9 ⁇ m).
• the paste composition was applied to a glass substrate (thickness 1 mm) by a screen printing method so as to have a thickness of 30 ⁇ m, and cured at 190 ° C. for 60 minutes.
• the volume resistivity of the obtained wiring was measured by the 4-terminal method using the product name "MCP-T600” (manufactured by Mitsubishi Chemical Corporation).
• [warp] A semiconductor produced by mounting a back gold silicon chip having a gold-deposited layer on an 8 mm ⁇ 8 mm joint surface on a copper substrate Ag-plated on the surface using a paste composition and curing it at 190 ° C. for 60 minutes.
• the package warpage of the package was measured at room temperature (25 ° C.).
• the measuring device was a shadow moiré measuring device (Thermore AXP: manufactured by Akrometrix), and the measurement was performed according to the JEITA ED-7306 standard of the Japan Electronics and Information Technology Industries Association.
• the maximum value in the direction perpendicular to the reference plane is A
• the minimum value is B
• Examples 1 to 9 using the paste composition containing silver particles of the present disclosure are all low in viscosity and excellent in dispersibility. It can be seen that the cured product of the paste composition has high thermal conductivity and little warpage. Further, it can be seen that all the semiconductor packages obtained by using the above paste composition have excellent adhesiveness with no chip peeling after the thermal cycle test.

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