WO2012070262A1 - 接合材料および接合体、並びに接合方法 - Google Patents

接合材料および接合体、並びに接合方法 Download PDF

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Publication number
WO2012070262A1
WO2012070262A1 PCT/JP2011/061089 JP2011061089W WO2012070262A1 WO 2012070262 A1 WO2012070262 A1 WO 2012070262A1 JP 2011061089 W JP2011061089 W JP 2011061089W WO 2012070262 A1 WO2012070262 A1 WO 2012070262A1
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Prior art keywords
bonding
bonding material
bonded
joining
joined
Prior art date
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PCT/JP2011/061089
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English (en)
French (fr)
Inventor
哲 栗田
圭一 遠藤
悠 齊藤
穣 久枝
俊彦 上山
Original Assignee
Ｄｏｗａエレクトロニクス株式会社
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Application filed by Ｄｏｗａエレクトロニクス株式会社 filed Critical Ｄｏｗａエレクトロニクス株式会社
Priority to EP11842826.7A priority Critical patent/EP2645408B1/en
Priority to US13/988,387 priority patent/US9486879B2/en
Priority to KR1020207016150A priority patent/KR102188054B1/ko
Priority to KR1020187000257A priority patent/KR102158290B1/ko
Priority to CN201180056112.3A priority patent/CN103250236B/zh
Priority to JP2012545628A priority patent/JP5986929B2/ja
Priority to KR1020137016031A priority patent/KR20130129392A/ko
Publication of WO2012070262A1 publication Critical patent/WO2012070262A1/ja

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    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/052—Metallic powder characterised by the size or surface area of the particles characterised by a mixture of particles of different sizes or by the particle size distribution
    • 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
    • B22F1/102—Metallic powder coated with organic material
    • 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
    • B23K1/00—Soldering, e.g. brazing, or unsoldering
    • B23K1/0008—Soldering, e.g. brazing, or unsoldering specially adapted for particular articles or work
    • B23K1/0016—Brazing of electronic components
    • 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
    • B23K20/00—Non-electric welding by applying impact or other pressure, with or without the application of heat, e.g. cladding or plating
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • 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
    • B23K31/00—Processes relevant to this subclass, specially adapted for particular articles or purposes, but not covered by only one of the preceding main groups
    • B23K31/02—Processes relevant to this subclass, specially adapted for particular articles or purposes, but not covered by only one of the preceding main groups relating to soldering or welding
    • 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
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    • 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
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Definitions

  • the present invention relates to a bonding material, a bonded body using the bonding material, and a bonding method.
  • a method of using silver brazing is considered as a bonding material and a bonding method candidate that can meet the requirements, but high temperature heating is required during the heat treatment operation.
  • electronic parts have been refined and miniaturized, and it is desired that the heating temperature during the joining operation be kept low. Under such circumstances, a bonding material and a bonding method using silver nanoparticles have attracted attention.
  • Non-Patent Document 1 a method of mixing silver oxide particles and myristyl alcohol to form a bonding material
  • Patent Document 2 a method of adding a carboxylic acid to a mixture of silver carbonate or silver oxide and silver nanoparticles, and bonding material
  • voids (hereinafter sometimes referred to as voids) are generated in the joining layer, which not only affects the joining strength of the joined body, but also joins. It was also found that it may affect the reliability of the body.
  • the present invention has been made under the above-mentioned circumstances, and the problem to be solved is a bonding that can form a bonded body even under an inert atmosphere such as nitrogen and can suppress the generation of voids. It is to provide a method and a bonding material.
  • the present inventors diligently studied to solve the above-described problems.
  • the joining material is applied to the joining surface of one member to be joined, and pre-baked, and then on the joining material layer.
  • Two bonding members are placed, main firing is performed, and a bonding layer is formed between one bonded member and the second bonded member.
  • the present invention was completed with the knowledge that generation can also be suppressed.
  • a bonding material composed of at least silver nanoparticles, silver particles, a flux, and a dispersion medium, which is coated with a fatty acid having 8 or less carbon atoms as the silver nanoparticles. If an average particle diameter of 0.5 ⁇ m to 10 ⁇ m is used and an organic substance having two or more carboxyl groups is used as a flux, bonding can be performed at 500 ° C. or lower in an inert atmosphere such as nitrogen. The epoch-making knowledge was acquired and the present invention was completed.
  • the first invention according to the present invention is: A joining method for joining a plurality of members to be joined, Applying a bonding material to a bonding surface of one bonded member; A pre-baking step of heating one member to which the bonding material is applied to a predetermined temperature; A step of installing the second member to be bonded on the layer of the bonding material applied to the heated one member to be bonded; One bonded member on which the second bonded member is installed is heated to a temperature higher than the temperature of the preliminary firing step, and a bonding layer is formed between the first bonded member and the second bonded member. And a main firing step.
  • the second invention is The bonding material is the bonding method according to the first invention, containing an organic substance having two or more carboxyl groups.
  • the third invention is The bonding material is the bonding method according to the first or second invention, wherein the bonding material contains silver nanoparticles having an average primary particle diameter of 1 nm to 200 nm.
  • the fourth invention is: In the main firing step, the joining method according to any one of the first to third inventions, wherein a pressure of 20 MPa or less is applied to a joining surface between one joined member and the second joined member.
  • the fifth invention is: Silver nanoparticles coated with a fatty acid having 8 or less carbon atoms and having an average primary particle diameter of 1 nm to 200 nm, silver particles having an average particle diameter of 0.5 ⁇ m to 10 ⁇ m, an organic substance having two or more carboxyl groups, A bonding material containing a dispersion medium.
  • the sixth invention is:
  • the organic material having two or more carboxyl groups is the bonding material according to the fifth invention having an ether bond.
  • the seventh invention The bonding material according to the fifth or sixth invention, wherein the organic substance having two or more carboxyl groups is oxydiacetic acid.
  • the eighth invention The bonding material according to any one of the fifth to seventh inventions, wherein the silver nanoparticles are coated with a fatty acid having 3 to 6 carbon atoms.
  • the ninth invention A joining method for joining a plurality of members to be joined, Applying the bonding material according to any one of the fifth to eighth inventions to a bonding surface of one bonded member; A pre-baking step of heating one member to which the bonding material is applied to a predetermined temperature; Installing a second member to be bonded on the layer of the bonding material applied to the heated one member to be bonded; One bonded member on which the second bonded member is installed is heated to a temperature higher than the temperature of the preliminary firing step, and a bonding layer is formed between the first bonded member and the second bonded member. And a main firing step.
  • the tenth invention is The joining method according to any one of the first to fourth and ninth inventions, wherein the main firing step is performed in an inert gas atmosphere.
  • An eleventh invention is the bonding method according to any one of the first to fourth, ninth, and tenth inventions, wherein the main firing step is performed at a temperature of 150 ° C. or higher and 500 ° C. or lower.
  • the twelfth invention The joining method according to any one of the first to fourth and ninth to eleventh inventions, wherein the heating rate of heating in the main firing step is 0.1 ° C./second or more and 2.0 ° C./second or less. is there.
  • the thirteenth invention A joined body in which a plurality of members to be joined are joined by a joining layer, and a void ratio existing in the joining layer is 2.0% or less.
  • the bonding material according to the present invention By using the bonding material according to the present invention, it is possible to form a bonded body that exhibits practical bonding strength at 500 ° C. or lower even in an inert atmosphere including nitrogen. In addition, according to the bonding method of the present invention, since voids are suppressed in the formed bonding layer, a bonded body exhibiting reliability and high strength can be obtained.
  • the silver nanoparticles, silver particles, flux, and dispersion medium constituting the bonding material according to the present invention will be described in detail, and then the manufacturing of the bonding material (paste) and the formation of the bonded body will be described.
  • the silver nanoparticles constituting the bonding material according to the present invention have an average primary particle diameter of 200 nm or less, preferably 1 to 150 nm, more preferably 10 to 100 nm. By using silver nanoparticles having the particle diameter, a bonded body having a strong bonding force can be formed.
  • the silver nanoparticles constituting the bonding material according to the present invention have a surface coated with an organic substance that is a protective agent.
  • the organic substance is preferably a fatty acid having a total carbon number of 8 or less.
  • saturated fatty acids such as octanoic acid (caprylic acid), heptanoic acid (enanthic acid), hexanoic acid (caproic acid), pentanoic acid (valeric acid), butanoic acid (butyric acid), propanoic acid (propionic acid), etc. Can be given.
  • dicarboxylic acid examples include oxalic acid, malonic acid, methylmalonic acid, ethylmalonic acid, succinic acid, methylsuccinic acid, ethylsuccinic acid, phenylsuccinic acid, glutaric acid, adipic acid, pimelic acid, and suberic acid.
  • unsaturated fatty acids include sorbic acid and maleic acid.
  • hexanoic acid, heptanoic acid, adipic acid, sorbic acid, and malonic acid are preferable from the viewpoint of productivity and workability, and silver in a powder form that is appropriately agglomerated by coating the surface of the silver nanoparticles with the fatty acid. Nanoparticles can be obtained.
  • the silver nanoparticles whose surface is coated with the fatty acid are in a form that can be easily collected as aggregates while maintaining the form of primary particles as silver nanoparticles.
  • the agglomerate has a particle size of at least 2.5 ⁇ m. This can be confirmed from the fact that the agglomerates can be recovered with No5C filter paper (JIS P-3801). That is, when this aggregate (secondary aggregate) is filtered using the above filter paper, the filtrate becomes clear, so the aggregate is considered to have a particle size larger than the aperture of the filter paper. Because it is. Furthermore, a dry powder composed of agglomerates of silver nanoparticles could be obtained by adding a low-temperature (less than 100 ° C.) drying operation to the recovered material.
  • the workability at the time of blending is greatly improved in producing the bonding material according to the present invention. Furthermore, it is possible to use silver nanoparticles coated with a plurality of kinds of organic substances, or to use silver nanoparticles having different average primary particle diameters in combination.
  • the addition amount of the silver nanoparticles is 10 to 80% by mass, preferably 15 to 75% by mass with respect to the total paste mass.
  • the silver nanoparticle which has the said particle diameter can be manufactured by the method of patent 4344001, for example.
  • the production method will be briefly described in the order of a liquid preparation step, a temperature raising step, a reaction step, an aging step, a filtration / washing step, and a drying step.
  • a reducing liquid in which a reducing substance is dissolved and a raw material liquid in which a metal salt (particularly a silver salt) as a raw material is dissolved are prepared.
  • the reducing solution is a homogeneous mixture of a reducing agent, a protective agent, and ammonia water as a stabilizer.
  • the reducing agent only needs to be capable of reducing the metal.
  • hydrazine hydrate, hydrazine, borohydride alkali salt (NaBH 4 etc.), lithium aluminum hydride (LiAlH 4 ), ascorbic acid, primary amine, secondary amine, tertiary amine etc. are used in combination You can also
  • the protective agent is an organic substance that adheres to the surface of the silver particles and inhibits the bonding between the particles as described above, and obtains stable fine silver particles.
  • the organic substance is preferably a fatty acid having a total carbon number of 8 or less, but it is particularly preferable to use hexanoic acid or sorbic acid.
  • Stabilizer is used for dissolving acid in water, and ammonia water can be used.
  • the solvent is preferably a polar solvent, and water or an organic solvent having a polar group can be used. Specific examples include water, alcohol, polyol, glycol ether, 1-methylpyrrolidinone, pyridine, terpineol, butyl carbitol, butyl carbitol acetate, texanol, and phenoxypropanol.
  • a specific example of the reducing solution is a mixture of water, hydrazine hydrated aqueous solution, hexanoic acid and aqueous ammonia
  • a specific example of the raw material solution is a silver nitrate aqueous solution.
  • the temperature of the reducing solution and the raw material solution is raised to the reaction temperature. At this time, it is preferable to heat the reducing solution and the raw material solution in the same manner, since there is an effect of preventing non-uniformity of the reaction during the reaction and the uniformity of the particles can be maintained.
  • the temperature raised at this time is in the range of 40 to 80 ° C.
  • the obtained slurry is solid-liquid separated by a filtration method.
  • the washing step is performed by adding pure water to the cake obtained in the filtration step and filtering the pure water again.
  • the nano-order primary fine particles form loose aggregates and settle naturally in the reaction solution, so that they can be easily recovered.
  • a dried metal (silver) particle mass is obtained by subjecting the obtained metal (silver) mass to a drying process at 60 to 90 ° C. for 6 to 24 hours.
  • the particle diameter of the silver nanoparticles is calculated from a transmission electron microscope (TEM) photograph. Specifically, 2 parts by mass of metal nanoparticles are added to a mixed solution of 96 parts by mass of cyclohexane and 2 parts by mass of oleic acid and dispersed by ultrasonic waves to obtain a dispersion solution. The obtained dispersion solution is dropped on a Cu microgrid with a support film and dried to prepare a TEM sample.
  • TEM transmission electron microscope
  • microgrid An image obtained by observing particles in a bright field using a transmission electron microscope (JEM-100CXMark-II type, manufactured by JEOL Ltd.) at a accelerating voltage of 100 kV is used for a microgrid, which is a prepared TEM sample, at a magnification of 300, You can shoot at 000 times.
  • JEM-100CXMark-II type manufactured by JEOL Ltd.
  • the particle diameter can be directly measured with calipers or the like, but can also be calculated by image software.
  • the average primary particle size of the silver nanoparticles is calculated by measuring at least 200 particles independently of each other in the TEM photograph and calculating the number average.
  • the silver particles constituting the bonding material according to the present invention have an average particle diameter in the range of 0.5 to 10 ⁇ m, preferably 0.5 to 9.0 ⁇ m, more preferably 0.5 to 8.0 ⁇ m. It is. There is no restriction
  • As a form of the silver particles various forms such as a spherical shape, a flake shape, a rectangular parallelepiped shape, a cubic shape, and an aggregate shape can be used.
  • the combined use of the submicron-order silver particles contributes to the improvement of the bonding strength of the bonding material, and a bonded body with high bonding strength can be obtained.
  • the addition amount of the silver particles is 10 to 80% by mass, preferably 15 to 75% by mass with respect to the total paste mass.
  • the average primary particle size of the silver particles may be measured by a laser diffraction method. For example, 0.3 g of a sample of silver particles is placed in 50 mL of isopropyl alcohol and dispersed for 5 minutes with an ultrasonic cleaner with an output of 50 W. For the dispersion, the value of D 50 (cumulative 50% by mass particle size) was measured by laser diffraction using a Microtrac particle size distribution analyzer (Honeywell-Nikkiso 9320-X100), and the value was averaged to the average. The particle size may be used.
  • the bonding material of the present invention is characterized in that a flux component (sintering acceleration component) made of an organic substance is added.
  • the flux component is an organic substance having two or more carboxyl groups. More preferably, it is a dicarboxylic acid further having an ether bond.
  • the flux component is preferably decomposed into a simple structure such as carbon dioxide or water. Therefore, it is preferable that the flux component is an organic substance composed of only elements such as carbon, hydrogen, and oxygen, and the decomposition temperature thereof is lower than the set temperature of the heat treatment operation. Specifically, it is 500 ° C. or lower, more preferably 300 ° C. or lower.
  • the molecular weight of the flux component is 1000 or less, preferably 500 or less, and more preferably 300 or less.
  • the total number of carbon atoms in the structure is at most 15 or less, preferably 10 or less.
  • a structure having such a molecular weight and carbon number can be decomposed or volatilized even if the bonding temperature is set at a relatively low temperature.
  • the organic substance having two or more carboxyl groups as the flux component include glycolic acid, which is an organic substance having a dicarboxylic acid structure, and oxydiacetic acid (diglycolic acid), which is a dicarboxylic acid having an ether bond. Can do.
  • the addition amount of the flux component is 0.01 to 1.0%, preferably 0.02 to 0.7%, and more preferably 0.05 to 0.5% with respect to the total paste mass.
  • the dispersion medium constituting the bonding material according to the present invention is preferably a polar solvent having a low vapor pressure from the viewpoint of dispersing silver nanoparticles. At this time, the dispersion medium does not necessarily need to be composed of one kind, and can be used in combination.
  • Specific examples include water, alcohol, polyol, glycol ether, 1-methylpyrrolidinone, pyridine, octanediol, terpineol, butyl carbitol, butyl carbitol acetate, texanol, phenoxypropanol, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, ⁇ -Butyrolactone, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, methoxybutyl acetate, methoxypropyl acetate, diethylene glycol monoethyl ether acetate, ethyl lactate, 1-octanol and the like.
  • the addition amount of the solvent in the total paste is 1 to 25%, preferably 3 to the total paste mass in consideration of printability and the like. 20%, more preferably 5 to 15%.
  • viscosity modifiers include hydrocarbon solvents, various fatty acids, water-soluble resins, aqueous dispersion resins, and inorganic binders.
  • naphthenic hydrocarbon solvent oleic acid, acrylic resin, maleic acid resin, fumaric acid resin, high acid value resin of styrene / maleic acid copolymer resin, polyester resin, polyolefin resin, phenoxy resin, polyimide resin, Polyamide resin or vinyl acetate emulsion, acrylic emulsion, synthetic rubber latex, epoxy resin, phenol resin, DAP resin, urethane resin, fluororesin, silicone resin, ethyl cellulose, polyvinyl alcohol, and the like can be added.
  • the inorganic binder include silica sol, alumina sol, zirconia sol, and titania sol.
  • the total amount of the viscosity modifier additive may have balance with other components, but is 0.2 to 2.0% by mass, preferably 0.3 to 1.5% by mass with respect to the total mass of the paste. More preferably, the content is 0.3 to 1.0% by mass.
  • any known method can be adopted as long as it does not involve significant modification of silver nanoparticles and silver particles.
  • Specific examples include ultrasonic dispersion, a disper, a three-roll mill, a ball mill, a bead mill, a twin-screw kneader, and a self-revolving stirrer, and these can be used alone or in combination.
  • the metallization temperature of the silver nanoparticles described above may vary greatly depending on the type of organic substance, dispersion medium, or additive that covers the surface. Therefore, it is preferable to grasp the thermal properties of the manufactured bonding material in advance by TG measurement or the like.
  • the joining material is applied to the surface of the substrate, which is one member to be joined, with a thickness of about 20 ⁇ m to 200 ⁇ m by, for example, a metal mask, dispenser, or screen printing method.
  • a metal mask, dispenser or screen printing method.
  • the object to be bonded which is a second member to be bonded
  • main baking a heat treatment step at high temperature
  • the bonding material according to the present invention is metallized even in the main firing at 500 ° C. or lower in an inert atmosphere including nitrogen, but even when the main material is fired in the air as in the conventional manufacturing method. Can be metallized.
  • the preliminary bonding to the bonding material applied to the substrate surface is performed under conditions lower than the decomposition temperature of the silver nanoparticles used in the bonding material and the boiling point of the dispersion medium. It is preferable to remove heat bubbles and gas by performing heat treatment as firing.
  • the preliminary firing is preferable because void formation in the bonding layer when the bonded body is formed can be suppressed, and as a result, the bonding strength of the bonding layer can be increased.
  • the pre-baking temperature is preferably in the range of 50 to 150 ° C., and preferably 50 to 350 ° C. lower than the temperature during the main baking. Further, although the pre-baking time depends on the area to be joined, about 10 minutes is sufficient, and heating for about 30 seconds may be sufficient.
  • the preliminary firing described above can suppress the generation of voids in the bonding layer even when applied to not only the bonding material according to the present invention but also the bonding material according to the prior art.
  • the object to be bonded is disposed on the upper part of the bonding material coating layer. And in order to form a joined body, it heats up, pressurizing a to-be-joined object to a board
  • the pressurizing pressure at this time can be appropriately set depending on the material to be joined. However, considering the influence on the object to be joined and the substrate, it is preferable to set the pressure to 20 MPa or less, preferably 15 MPa or less.
  • the temperature at the time of forming the bonding layer in the main firing is preferably 150 ° C to 500 ° C.
  • the main firing temperature can also be set as appropriate depending on the type of the bonded product or substrate to be bonded.
  • the heating rate in the main firing is 0.1 to 2.0 ° C./second, preferably 0.2 to 1.5 ° C./second. By taking the temperature increase rate, a dense bonding layer can be formed, and a stable bonded body can be obtained.
  • Example 1 ⁇ Synthesis of silver nanoparticles> Using a 500 mL beaker, 13.4 g of silver nitrate (manufactured by Toyo Chemical Co., Ltd.) was dissolved in 72.1 g of pure water to prepare a raw material solution.
  • the mixture was aged for 30 minutes to form silver nanoparticle aggregates coated with sorbic acid. Then, the liquid in which the silver nanoparticle aggregate was formed was filtered with the filter paper of No5C, and the collect
  • the mixture was kneaded for 30 seconds (kneading conditions / Revolution; 1400 rpm, Rotation; 700 rpm) with a kneading defoaming machine (EME V-mini300 type), and then with a three-roll (EXAKApparatebaus 22851 Nordestedt type).
  • the bonding material (paste) according to Example 1 was obtained after five passes.
  • Tables 1 and 2 show the composition of the bonding material according to Example 1. Note that octanediol has a boiling point of 244 ° C. and a flash point of 135 ° C.
  • a metal mask (mask thickness 50 ⁇ m) was prepared, and the joining material (paste) according to Example 1 was applied by a printing method onto a silver-plated copper substrate by manual printing with a metal squeegee.
  • the pattern was ⁇ 5.5 mm and 50 ⁇ m thick.
  • the copper substrate coated with the bonding material thus obtained was placed in a furnace (flip chip bonder M-90, manufactured by DON-400 Hisol Co., Ltd.) and heated at 100 ° C. for 10 minutes in a nitrogen atmosphere (oxygen concentration: 500 ppm or less). Then, preliminary firing was performed to remove bubbles and gas components in the bonding material.
  • the copper substrate on which the bonding material was applied was cooled to 25 ° C., and a chip (a silver-plated Si chip with 5 mm square and 0.3 mm thickness) was mounted on the coated surface.
  • the copper substrate on which the chip is mounted is placed in the furnace again, pressurized at 10 MPa, heated to 250 ° C. at a heating rate of 1 ° C./second, and after firing reaches 250 ° C. for 5 minutes. Holding, the joined body according to Example 1 was obtained.
  • Measurement of the joining force of the joined body according to Example 1 was performed. Specifically, it was carried out in accordance with the method described in “Lead-free solder test method, part 5 solder joint tensile and shear test method” of JISZ-03918-5: 2003. That is, it is a method of measuring the force when the bonded surface breaks in such a way that the object to be bonded (chip) bonded on the substrate is pushed in the horizontal direction and cannot withstand the pressed force.
  • a test was performed using a DAGE bond tester (series 4000). The share height was 50 ⁇ m, the test speed was 5 mm / min, and the measurement was performed at room temperature.
  • the bonding strength (average shear strength) between the substrate and the chip in the bonded body according to Example 1 was 64.0 MPa.
  • the abundance ratio of voids inside the joined body according to Example 1 was measured by X-ray measurement (X-ray fluoroscopy device SMX-160LT manufactured by Takashimazu Seisakusho). Specifically, using the image analysis software, adjust the brightness range (color range) so that the voids are colored red, and binarize the area of ⁇ 5 mm to make the void area ratio Is calculated. The results are shown in Tables 1 and 2.
  • Example 2 Except for changing the addition amount of octanediol, which is a dispersion medium of the bonding material according to Example 1, to 7.95 g and further adding 2.0 g of EXXSOL D130 FLUID (manufactured by ExxonMobil) for the purpose of viscosity adjustment,
  • the bonding material according to Example 2 was manufactured through the same manufacturing process as in Example 1. And through the process similar to Example 1, the joined body which concerns on Example 2 was formed, and evaluation similar to Example 1 was performed. The evaluation results are shown in Tables 1 and 2.
  • Example 3 Except that the silver powder of the joining material according to Example 1 was changed from spherical silver particles to flake silver particle powder (FA-D-6 manufactured by DOWA Electronics Co., Ltd .: average primary particle diameter (D 50 ) 8.3 ⁇ m).
  • the bonding material according to Example 3 was manufactured through the same manufacturing process as in Example 1. And through the process similar to Example 1, the joined_body
  • Example 4 From the silver nanoparticle aggregate dried powder coated with sorbic acid (average primary particle size: 100 nm) of the bonding material according to Example 1, the silver nanoparticle aggregate dried powder coated with sorbic acid (average primary particle size: 60 nm), the flux is 0.1 g of oxydiacetic acid (manufactured by Wako Pure Chemical Industries, Ltd .: diglycolic acid), and octanediol (manufactured by Kyowa Hakko Chemical Co., Ltd .: 2-ethyl-1,3-hexanediol) as a dispersion medium
  • the joining material which concerns on Example 4 was manufactured through the manufacturing process similar to Example 1 except having changed the addition amount of 9.9g. And through the process similar to Example 1, the joined body which concerns on Example 4 was formed, and evaluation similar to Example 1 was performed. The evaluation results are shown in Tables 1 and 2.
  • Example 5 The addition amount of octanediol which is a dispersion medium of the bonding material according to Example 1 was changed to 7.45 g, and 2.0 g of EXXSOL D130 FLUID (manufactured by ExxonMobil) was added for the purpose of adjusting the viscosity.
  • a bonding material according to Example 5 was manufactured through the same manufacturing process as Example 1 except that 0.5 g of oleic acid (manufactured by Kishida Chemical Co., Ltd.) was added for the purpose of adjusting the viscosity.
  • the joined body which concerns on Example 5 was formed, and evaluation similar to Example 1 was performed. The evaluation results are shown in Tables 1 and 2.
  • Example 1 A bonding material according to Example 1 was prepared. Then, without pre-baking before chip mounting, the chip is mounted on a copper substrate coated with a bonding material, pressurized at 10 MPa, heated at 100 ° C. for 10 minutes as preliminary drying, and then heated to 250 ° C. The temperature was increased at a rate of 1 ° C./second, and after the temperature reached 250 ° C. for main baking, the bonded body according to Comparative Example 1 was formed, and the same evaluation as in Example 1 was performed. The evaluation results are shown in Tables 1 and 2.
  • Comparative Example 2 Using the bonding material according to Example 2, the bonded body according to Comparative Example 2 was formed through the same process as in Comparative Example 1, and the same evaluation as in Example 1 was performed. The evaluation results are shown in Tables 1 and 2.
  • Comparative Example 3 Using the bonding material according to Example 3, the bonded body according to Comparative Example 3 was formed through the same steps as in Comparative Example 1, and the same evaluation as in Example 1 was performed. The evaluation results are shown in Tables 1 and 2.
  • FIG. 1 shows the bonding strength of the bonded bodies according to Examples 1 to 3 and Comparative Examples 1 to 3.
  • FIG. 1 is a bar graph in which the vertical axis represents the bonding strength (shear strength) and the horizontal axis represents Example 1-Comparative Example 1, Example 2-Comparative Example 2, and Example 3-Comparative Example 3.
  • Example 3—Comparative Example 3 use a paste of the same composition as the bonding material. Firing was performed, and in Comparative Examples 1 to 3, preliminary firing before chip mounting was not performed. From FIG. 1, the joined bodies according to Examples 1 to 3 that were pre-fired before chip mounting were joined to 2.3 to 6.2 than the joined bodies according to Comparative Examples 1 to 3 that were not pre-fired. It has been found that it exhibits strength.
  • a bonding material and a bonding body, and a bonding method according to the present invention include a non-insulated semiconductor device, application to a bare chip mounting assembly technology, a power device (IGBT, rectifier diode, power transistor, power MOSFET, insulated gate bipolar transistor, thyristor, It can be applied to gate turn-off thyristors and triacs, and can also be applied to bonding materials on glass whose surface is chrome-treated, and can also be applied to bonding materials for electrodes and frames of lighting devices using LEDs. It is.
  • IGBT rectifier diode
  • power transistor power MOSFET
  • insulated gate bipolar transistor thyristor

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Abstract

　窒素を初めとした不活性雰囲気下での接合体形成が可能であり、かつ高温の熱処理操作を行わずとも実用に耐えうる接合強度を発揮する接合材料を提供すること。炭素数８以下の脂肪酸で被覆され平均一次粒子径が１ｎｍ以上２００ｎｍ以下の銀ナノ粒子と、平均粒子径が０．５μｍ以上１０μｍ以下の銀粒子と、２以上のカルボキシル基を有する有機物質と、分散媒とを含む接合材料を提供する。

Description

接合材料および接合体、並びに接合方法
　本発明は、接合材料およびそれを用いた接合体、並びに接合方法に関する。
　自動車や産業機器に用いる電子部品へ流れる電流の増大傾向に伴い、当該電子部品内部に使用される半導体の動作温度は高温になる傾向にある。その為、当該電子部品では高温環境に耐えうる接合材料が要望されるようになってきた。当該要望に対し、従来は高温でも強度を維持する鉛含有はんだが使用されてきた。しかし、昨今の鉛使用抑制の趨勢から、鉛含有はんだを使用しない接合方法が求められている。
　当該要求に対応可能な接合材料、接合方法の候補として、銀ろうを用いる方法が考えられるが、熱処理操作時に高温加熱が必要となる。一方、電子部品は、精密化、微細化が進行し、接合操作時の加熱温度は、低く抑えることが要望されている。当該状況下において、銀ナノ粒子を用いた接合材料、接合方法が着目されている。
　例えば、酸化銀粒子とミリスチルアルコールとを混合して接合材料となす方法（非特許文献１、特許文献１）、炭酸銀または酸化銀と銀ナノ粒子との混合物へカルボン酸を添加して接合材料とする方法（特許文献２）等が提案されている。
特開２００９－２６７３７４号公報 特開２００９－２７９６４９号公報
守田ら　「マイクロメートルサイズの酸化銀粒子を用いた高温環境向け鉛フリー接合技術の開発」　まてりあ　第４９巻　第１号（２０１０）
　上述した特許文献にも記載されているように、従来の技術に係る接合材料を用いて接合体を形成する際、当該接合操作は含酸素雰囲気である大気中で行なわれている。
　本発明者らは、当該接合操作を大気中で行うと、接合体の界面部に存在する接合材料に由来する銀が酸化銀となり、接合材料の接合力へ悪影響を及ぼす可能性があることに想到した。なかでも、微細な構造を有する接合体においては、こうした悪影響は顕著となると考えられた。
　そこで、当該接合操作を、窒素を初めとした不活性雰囲気下で行うことを考えた。ところが、従来の技術に係る接合材料を用いて、窒素を初めとした不活性雰囲気下で接合操作を行なった場合、条件により十分な強度が得られないことが知見された。
　さらに、従来の技術に係る接合方法を用いた場合、接合層中に空孔（以降、ボイドと記載する場合もある。）が生成し、接合体の接合強度に影響を与えるだけでなく、接合体の信頼性にも影響を与える場合があることも知見された。
　本発明は、上述の状況の下で為されたものであり、その解決しようとする課題は、窒素を初めとした不活性雰囲気下でも接合体形成が可能であり、ボイドの発生を抑制できる接合方法と、接合材料とを提供することである。
　本発明者らは、上述の課題を解決すべく鋭意検討したところ、接合操作において、一の被接合部材の接合面へ接合材料を塗布し、予備焼成を行なった後に、接合材料の層上へ二の被接合部材を配置して、本焼成を行ない、一の被接合部材と二の被接合部材との間に接合層を形成するという接合方法により、実用に耐える強度を発揮すると同時に、ボイド生成も抑制出来るとの知見を得て本発明を完成した。
　そして、少なくとも銀ナノ粒子と、銀粒子と、フラックスと、分散媒とから構成される接合材料であって、当該銀ナノ粒子として炭素数８以下の脂肪酸で被覆されたものを用い、銀粒子として平均粒子径が０．５μｍ～１０μｍのものを用い、フラックスとして２以上のカルボキシル基を有する有機物質を用いれば、窒素を初めとした不活性雰囲気下において、５００℃以下でも接合が可能になるとの画期的な知見を得、本発明を完成させた。
　即ち、本発明に係る第１の発明は、
　複数の被接合部材を接合する接合方法であって、
　一の被接合部材の接合面へ接合材料を塗布する工程と、
　接合材料を塗布された一の被接合部材を、所定の温度に加熱する予備焼成工程と、
　加熱された一の被接合部材に塗布された接合材料の層上へ、二の被接合部材を設置する工程と、
　二の被接合部材が設置された一の被接合部材を、前記予備焼成工程の温度より高い温度に加熱して、一の被接合部材と二の被接合部材との間に接合層を形成する本焼成工程とを有する接合方法である。
　第２の発明は、
　前記接合材料は、２以上のカルボキシル基を有する有機物質を含有する第１の発明に記載の接合方法である。
　第３の発明は、
　前記接合材料は、少なくとも平均一次粒子径が１ｎｍ以上２００ｎｍ以下の銀ナノ粒子を含有する、第１または第２の発明に記載の接合方法である。
　第４の発明は、
　前記本焼成工程において、一の被接合部材と二の被接合部材との接合面へ２０ＭＰａ以下の加圧を行なう第１ないし第３の発明のいずれかに記載の接合方法である。
　第５の発明は、
　炭素数８以下の脂肪酸で被覆され平均一次粒子径が１ｎｍ以上２００ｎｍ以下の銀ナノ粒子と、平均粒子径が０．５μｍ以上１０μｍ以下の銀粒子と、２以上のカルボキシル基を有する有機物質と、分散媒とを含む接合材料である。
　第６の発明は、
　前記２以上のカルボキシル基を有する有機物質が、エーテル結合を有する第５の発明に記載の接合材料である。
　第７の発明は、
　前記２以上のカルボキシル基を有する有機物質が、オキシジ酢酸である第５または第６の発明に記載の接合材料である。
　第８の発明は、
　前記銀ナノ粒子が、炭素数３以上６以下の脂肪酸で被覆されている第５ないし第７の発明のいずれかに記載の接合材料である。
　第９の発明は、
　複数の被接合部材を接合する接合方法であって、
　一の被接合部材の接合面へ第５ないし第８の発明のいずれかに記載の接合材料を塗布する工程と、
　前記接合材料を塗布された一の被接合部材を、所定の温度に加熱する予備焼成工程と、
　加熱された一の被接合部材に塗布された前記接合材料の層上へ、二の被接合部材を設置する工程と、
　二の被接合部材が設置された一の被接合部材を、前記予備焼成工程の温度より高い温度に加熱して、一の被接合部材と二の被接合部材との間に接合層を形成する本焼成工程とを有する接合方法である。
　第１０の発明は、
　前記本焼成工程を不活性ガス雰囲気下で行う第１ないし第４、第９の発明のいずれかに記載の接合方法である。
　第１１の発明は
　前記本焼成工程を１５０℃以上５００℃以下の温度で行う第１ないし第４、第９または第１０の発明のいずれかに記載の接合方法である。
　第１２の発明は、
　前記本焼成工程における加熱の昇温速度を、０．１℃／秒以上２．０℃／秒以下で行う第１ないし第４、第９ないし第１１の発明のいずれかに記載の接合方法である。
　第１３の発明は、
　複数の被接合部材が接合層により接合された接合体であって、当該接合層に存在するボイド率が２．０％以下である接合体である。
　本発明に係る接合材料を使用することにより、特に窒素を初めとした不活性雰囲気下でも５００℃以下で、実用的な接合強度を発揮する接合体を形成することが出来る。また、本発明に係る接合方法によれば、形成される接合層の内部でボイドの発生が抑制されるので、信頼性と高強度を発揮する接合体を得ることが出来る。
実施例および比較例に係る接合体の接合強度を示すグラフである。
　まず、本発明に係る接合材料を構成する銀ナノ粒子、銀粒子、フラックス、および分散媒について詳細に説明し、次いで、接合材料（ペースト）の製造、接合体の形成について説明する。
＜銀ナノ粒子＞
　本発明に係る接合材料を構成する銀ナノ粒子は、平均一次粒子径が２００ｎｍ以下、好ましくは１～１５０ｎｍ、一層好ましくは１０～１００ｎｍのものである。当該粒子径を有する銀ナノ粒子を使用することで、強い接合力を有した接合体を形成することができる。
　本発明に係る接合材料を構成する銀ナノ粒子は、表面が保護剤である有機物質で被覆されている。当該有機物質は全炭素数が８以下である脂肪酸が好ましい。具体的には、飽和脂肪酸であるオクタン酸（カプリル酸）、ヘプタン酸（エナント酸）、ヘキサン酸（カプロン酸）、ペンタン酸（吉草酸）、ブタン酸（酪酸）、プロパン酸（プロピオン酸）などがあげられる。また、ジカルボン酸として、シュウ酸、マロン酸、メチルマロン酸、エチルマロン酸、コハク酸、メチルコハク酸、エチルコハク酸、フェニルコハク酸、グルタル酸、アジピン酸、ピメリン酸、スベリン酸等があげられる。不飽和脂肪酸では、ソルビン酸、マレイン酸等があげられる。
　なかでも、生産性、作業性の観点から、ヘキサン酸、ヘプタン酸、アジピン酸、ソルビン酸、マロン酸が好ましく、当該脂肪酸で銀ナノ粒子表面を被覆することで、適度に凝集した粉末形態の銀ナノ粒子を得ることが出来る。
　当該脂肪酸で表面が被覆された銀ナノ粒子は、銀ナノ粒子として一次粒子の形態を保ちながら、凝集塊となって容易に回収できうる形態となっている。当該凝集塊の粒径は少なくとも２．５μｍ以上である。これは、当該凝集塊が、Ｎｏ５Ｃ濾紙（ＪＩＳ　Ｐ－３８０１）で回収可能であることから確認することが出来る。つまり、この凝集塊（二次凝集）を、上記濾紙を用いて濾別すると、濾液が清澄なものとなることから、凝集塊はその濾紙の目開き以上の粒子径を有していると考えられるからである。さらに、当該回収物へ低温（１００℃未満）の乾燥操作を加えることで、銀ナノ粒子の凝集塊からなる乾燥粉末を得ることもできた。
　銀ナノ粒子を粉末の形態を有するものとしたことにより、本発明に係る接合材料を製造するにあたり、配合時の作業性が大きく向上する。さらに、複数種の有機物質により被覆された銀ナノ粒子を使用すること、もしくは異なる平均一次粒子径を有した銀ナノ粒子を併用することも可能である。接合材料とする際、当該銀ナノ粒子の添加量としては全ペースト質量に対して１０～８０質量％、好ましくは１５～７５質量％とするとよい。
　ここで、当該粒子径を有する銀ナノ粒子は、例えば特許第４３４４００１号に記載の方法により製造することが出来る。当該製造方法について、調液工程、昇温工程、反応工程、熟成工程、濾過・洗浄工程および乾燥工程の順で、簡単に説明する。
《調液工程》
　還元性を有する物質を溶解させた還元液と、原料である金属塩（特に銀塩）が溶解された原料液とを準備する。
　還元液は、還元剤、保護剤および安定化剤のアンモニア水を均一混合したものである。尤も、還元剤は金属を還元可能なものであればよい。例えば、ヒドラジン水和物、さらに、ヒドラジン、水素化ホウ素アルカリ塩（ＮａＢＨ4など）、リチウムアルミニウムハイドライド（ＬｉＡｌＨ4）、アスコルビン酸、第一級アミン、第二級アミン、第三級アミンなどを併用することもできる。
　保護剤は、上述したように銀粒子の表面に付着し粒子同士の結合を阻害する有機物質で、安定した微小銀粒子を得るものである。当該有機物質は全炭素数が８以下である脂肪酸が好ましいが、なかでもヘキサン酸やソルビン酸を用いることが好適である。
　安定化剤は、水中に酸を溶解させるためのものでアンモニア水を用いることができる。
　溶媒は極性溶媒が好ましく、水または極性基を有する有機溶媒が使用できる。具体的には、水、アルコール、ポリオール、グリコールエーテル、１－メチルピロリジノン、ピリジン、ターピネオール、ブチルカルビトール、ブチルカルビトールアセテート、テキサノール、フェノキシプロパノールなどが例示できる。
　以上より、還元液の具体例は、水とヒドラジン水和水溶液とヘキサン酸とアンモニア水の混合物であり、原料液の具体例は、硝酸銀水溶液である。
《昇温工程》
　還元液と原料液とを昇温し、反応温度まで上昇させる。このとき、還元液と原料液とを、同様に加熱しておけば、反応時において反応の不均一が防止される効果があり、粒子の均一性を保つことができるので好ましい。このときに昇温させる温度は４０～８０℃の範囲である。
《反応工程》
　還元液と原料液とが目的温度まで上昇したら、還元液に対して原料液を添加する。添加は突沸に注意した上で、一挙に添加することが好ましい。
《熟成工程》
　還元液と原料液とを混合した後、１０～３０分間程度攪拌を続け、粒子の成長を完結させる。
《濾過・洗浄工程》
　得られたスラリーは濾過法により固液分離する。洗浄工程は、当該濾過工程で得られたケーキに対して純水を加え、再び該純水を濾過することによって行う。本発明の製造法によれば、ナノオーダーの一次微粒子が緩やかな凝集体を形成し、反応液中に自然に沈降するため、容易に回収できる。
《乾燥工程》
　得られた金属（銀）塊へ６０～９０℃、６～２４時間の乾燥工程を施すことで、乾燥した金属（銀）粒子塊が得られる。
《銀ナノ粒子の測定・評価》
　銀ナノ粒子の粒子径は、透過型電子顕微鏡（ＴＥＭ）写真から算出される。
　具体的には、金属ナノ粒子２質量部を、シクロヘキサン９６質量部とオレイン酸２質量部との混合溶液に添加し、超音波によって分散させて分散溶液を得る。得られた分散溶液を、支持膜付きＣｕマイクログリッドに滴下し、乾燥させることでＴＥＭ試料を作成する。作成したＴＥＭ試料であるマイクログリッドを、透過型電子顕微鏡（日本電子株式会社製ＪＥＭ－１００ＣＸＭａｒｋ－ＩＩ型）を用い、１００ｋＶの加速電圧にて、明視野で粒子を観察した像を、倍率３００，０００倍で撮影すれば良い。
　得られた銀ナノ粒子のＴＥＭ写真像から、直接ノギス等による粒子径測定も可能だが、画像ソフトにより算出することもできる。いずれにしても、銀ナノ粒子の平均一次粒子径は、ＴＥＭ写真中における個々に独立した粒子について、少なくとも２００個測定し、その数平均で算出する。
＜銀粒子＞
　本発明に係る接合材料を構成する銀粒子は、平均粒子径の範囲が０．５～１０μｍ、好ましくは０．５～９．０μｍ、一層好ましくは０．５～８．０μｍの範囲の銀粒子である。銀粒子の形態については、特に制限はない。銀粒子の形態としては、球状、フレーク（鱗片）状、直方体状、立方体状、凝集体状といった様々な形態が使用できる。
　上述した銀ナノ粒子に加えて、当該サブミクロンオーダーの銀粒子を併用することにより、接合材料の接合強度の向上に寄与し、接合力の高い接合体を得ることができる。接合材料とする際、当該銀粒子の添加量としては全ペースト質量に対して１０～８０質量％、好ましくは１５～７５質量％とするとよい。
　当該銀粒子の平均一次粒子径測定は、レーザー回折法によれば良い。例えば、銀粒子の試料０．３ｇをイソプロピルアルコール５０ｍＬに入れ、出力５０Ｗの超音波洗浄機で５分間分散させる。当該分散液に対し、マイクロトラック粒度分布測定装置（ハネウエル－日機装製の９３２０－Ｘ１００）を用いてレーザー回折法でＤ50（累積５０質量％粒子径）の値を測定し、当該値を平均一次粒子径とすれば良い。
＜フラックス＞
　本発明の接合材料は、有機物からなるフラックス成分（焼結促進成分）を添加することを特徴とする。ここでフラックス成分とは、具体的に述べれば、２以上のカルボキシル基を有する有機物質である。より好ましくは、さらにエーテル結合を有するジカルボン酸である。接合材料へ当該構成を有するフラックス成分を添加することにより、窒素を初めとした不活性雰囲気下における５００℃以下の熱処理操作であっても、上述した有機物質で被覆された銀ナノ粒子を、バルク態の銀に変化させることが出来る。
　上述した熱処理操作の際、当該フラックス成分は、二酸化炭素や水等の単純な構成に分解されることが好ましい。従って、当該フラックス成分は、炭素、水素、酸素といった元素のみで構成されている有機物質であって、その分解温度が熱処理操作の設定温度以下であることが好ましい。具体的には５００℃以下、より好ましくは３００℃以下である。
　当該観点から、当該フラックス成分の分子量は１０００以下、好ましくは５００以下、一層好ましくは３００以下である。また、構造中における合計炭素数は、多くとも１５以下、好ましくは１０以下であるのがよい。この程度の分子量および炭素数を有する構造であれば、比較的低温である接合温度に設定しても分解または揮散させることができる。
　当該フラックス成分である２以上のカルボキシル基を有する有機物質の好ましい例として、ジカルボン酸構造を有する有機物質であるグリコール酸、さらにエーテル結合を有するジカルボン酸であるオキシジ酢酸（ジグリコール酸）を挙げることができる。このとき、フラックス成分の添加量は全ペースト質量に対して０．０１～１．０％、好ましくは０．０２～０．７％、一層好ましくは０．０５～０．５％である。
＜分散媒＞
　本発明に係る接合材料を構成する分散媒は、銀ナノ粒子を分散させる観点から蒸気圧が低い極性溶媒とすることが好ましい。なお、この時分散媒は必ずしも一種類で構成する必要はなく、併用混合することも出来る。
　具体例としては、水、アルコール、ポリオール、グリコールエーテル、１－メチルピロリジノン、ピリジン、オクタンジオール、ターピネオール、ブチルカルビトール、ブチルカルビトールアセテート、テキサノール、フェノキシプロパノール、ジエチレングリコールモノブチルエーテル、ジエチレングリコールモノブチルエーテルアセテート、γ―ブチロラクトン、エチレングリコールモノメチルエーテルアセテート、エチレングリコールモノエチルエーテルアセテート、メトキシブチルアセテート、メトキシプロピルアセテート、ジエチレングリコールモノエチルエーテルアセテート、乳酸エチル、１－オクタノール等が挙げられる。全ペースト中の当該溶媒の添加量（２種以上を混合するときは、当然合計量である。）は、印刷性等を考慮して全ペースト質量に対して１～２５％、好ましくは３～２０％、一層好ましくは５～１５％である。
＜その他の添加剤＞
　上述した分散媒へ、銀ナノ粒子の焼結温度低下や密着の促進を図る添加剤や、粘度調整剤を添加することも好ましい構成である。
　粘度調整剤の例としては、炭化水素溶剤、各種の脂肪酸、水溶化樹脂、水性分散樹脂、および無機バインダーがある。具体的には、ナフテン系炭化水素溶剤、オレイン酸、アクリル樹脂、マレイン酸樹脂、フマル酸樹脂、スチレン・マレイン酸共重合樹脂の高酸価樹脂、ポリエステル樹脂、ポリオレフィン樹脂、フェノキシ樹脂、ポリイミド樹脂、ポリアミド樹脂あるいは酢酸ビニル系エマルション、アクリルエマルション、合成ゴムラテックス、エポキシ樹脂、フェノール樹脂、ＤＡＰ樹脂、ウレタン樹脂、フッ素樹脂、シリコーン樹脂、エチルセルロースおよびポリビニルアルコール等を添加することができる。無機バインダーの例としては、シリカゾル、アルミナゾル、ジルコニアゾル、チタニアゾルといったものを挙げることが出来る。
　当該粘度調整剤の添加により、ペーストを基板へ印刷した際に、転写性の改善や、かすれ等の抑制等のいわゆる印刷性の改善効果が期待される。
　尤も、こうした粘度調整剤は、焼結性を改善する観点から添加量が少ない方が好ましい。そこで、当該粘度調整剤の添加剤の総量は、他成分との兼ね合いもあるが、ペーストの総質量に対して０．２～２．０質量％、好ましくは０．３～１．５質量％、一層好ましくは０．３～１．０質量％とするのがよい。
＜接合材料（ペースト）の製造＞
　本発明に係る接合材料の製造方法について説明する。当該混合物を混練脱泡機へ導入して混練し混練物を形成させる。その後、当該混練物へ機械的分散処理を行い本発明に係る接合材料を得る。
　当該機械的分散処理は、銀ナノ粒子および銀粒子の著しい改質を伴わないとものであれば、公知のいずれの方法も採用することが可能である。具体的には、超音波分散、ディスパー、三本ロールミル、ボールミル、ビーズミル、二軸ニーダー、自公転式攪拌機などが例示でき、これらは単独あるいは複数を併用して使用することもできる。
　上述した銀ナノ粒子の金属化温度は、その表面を被覆する有機物質や分散媒、または添加物の種類により、大きく変化する場合が有る。そこで、製造された接合材料において、予めＴＧ測定などにより熱的性質を把握しておくことが好ましい。
＜接合体の形成＞
　接合体の形成は、接合部が形成される一の被接合部材である基板表面へ、例えばメタルマスク、ディスペンサーまたはスクリーン印刷法により、２０μｍ～２００μｍ程度の厚みで接合材料を塗布する。塗布後、低温による熱処理（以降、予備焼成という）を経た後、二の被接合部材である被接合物を貼付し、高温による熱処理工程（以降は、本焼成という。）により接合材料を金属化する。
　本発明に係る接合材料は、窒素を初めとした不活性雰囲気下における５００℃以下の本焼成であっても金属化するが、従来の製造法と同じく大気中で本焼成した場合であっても金属化することができる。
　ここで、基板表面に塗布された接合材料中に気泡が存在したり、ガスが含まれていると、形成された接合層においてボイドが生成する原因となる。そこで、当該接合材料中の気泡やガスを除く為、接合材料に用いられている銀ナノ粒子の分解温度や分散媒の沸点よりも低温の条件で、基板表面に塗布された接合材料へ、予備焼成として熱処理を行い気泡やガスを除くことが好ましい。当該予備焼成の実施により、接合体を形成した際の接合層におけるボイドの生成を抑制することができ、ひいては接合層の接合強度を高めることが出来るので好ましい。
　一般的に、予備焼成温度は５０～１５０℃の範囲であって、かつ、本焼成の際の温度よりも５０～３５０℃低い温度とするのが好ましい。また、予備焼成時間はその接合対象面積に依存するが、おおよそ１０分間程度あれば十分で、３０秒間程度の加熱であっても構わない場合もある。
　以上説明した予備焼成は、本発明に係る接合材料のみならず、従来の技術に係る接合材料へ適用した場合であっても、接合層中のボイドの生成を抑制することが出来る。
　予備焼成の後、接合材料の塗布層上部へ被接合物を配設する。そして、接合体を形成する為、被接合物を基板へ加圧しながら昇温する。この時の加圧圧力は、その接合する材料により適宜設定することが出来る。尤も、接合される被接合物や基板への影響を考慮すると、２０ＭＰａ以下、好ましくは１５ＭＰａ以下とすることが好ましい。
　本焼成における接合層形成時における温度は、１５０℃以上５００℃以下の低温で行うことが好ましい。当該本焼成温度も接合される接合物や基板の種類により適宜設定可能である。そして、本焼成における昇温速度は０．１～２．０℃／秒、好ましくは０．２～１．５℃／秒である。当該昇温速度をとることで、緻密な接合層を形成することが出来、安定した接合体を得ることが出来る。
　さらに、当該本焼成温度を６０分間～３０分間保持して接合層中における銀粒子の金属化を進めれば、より強固な接合層を得ることが出来る。
　以下、実施例を参照しながら、本発明をより具体的に説明する。
［実施例１］
　＜銀ナノ粒子の合成＞
　５００ｍＬビーカーを用い、硝酸銀（東洋化学株式会社製）１３．４ｇを純水７２．１ｇへ溶解させて原料液を調製した。
　一方、５Ｌビーカーに１．４Ｌの純水を仕込み、ここへ窒素を３０分間通気させて溶存酸素を除去しつつ、４０℃まで昇温した。そして、当該純水へ保護剤としてソルビン酸（和光純薬工業株式会社製）１７．９ｇを添加し、次に、安定化剤として２８％アンモニア水（和光純薬工業株式会社製）２．８ｇを添加した。
　以後の実施例、比較例ともに、このアンモニア水添加時点をもって、反応開始時とした。
　当該アンモニア添加溶液の攪拌を継続し、反応開始５分経過後に還元剤として含水ヒドラジン（純度８０％：大塚化学株式会社製）６．０ｇを添加して、還元液を調製した。反応開始１０分経過後に、液温を４０℃に調整した原料液を、還元液へ一挙に添加して反応させ、撹拌を終了した。
　撹拌終了後、３０分熟成してソルビン酸で被覆された銀ナノ粒子凝集体を形成させた。その後、銀ナノ粒子凝集体が形成された液をＮｏ５Ｃのろ紙で濾過し、回収物を純水で洗浄して、銀ナノ粒子凝集体を得た。当該銀ナノ粒子凝集体を、真空乾燥機中で８０℃１２時間の条件で乾燥させ、銀ナノ粒子凝集体の乾燥粉を得た。
〈接合材料の調製〉
　得られたソルビン酸が被覆された銀ナノ粒子凝集体乾燥粉（平均一次粒子径：１００ｎｍ）４５．０ｇ（全銀中の割合は５０．００質量％）を銀ナノ粒子粉とし、球状銀粒子の粉末（ＤＯＷＡエレクトロニクス株式会社製　２－１Ｃ球状銀粉末：平均一次粒子径（Ｄ50）１．０μｍ）４５．０ｇ（全銀中の割合は５０．００質量％）と、フラックスとしてオキシジ酢酸（和光純薬株式会社製：ジグリコール酸）０．０５ｇと、分散媒としてオクタンジオール（協和発酵ケミカル社製：２－エチル－１，３－ヘキサンジオール）９．９５ｇとを、混合し、混合物とした。
　当該混合物を、混練脱泡機（ＥＭＥ社製　Ｖ－ｍｉｎｉ３００型）で３０秒間（混練条件／Ｒｅｖｏｌｕｔｉｏｎ；１４００ｒｐｍ、Ｒｏｔａｔｉｏｎ；７００ｒｐｍ）で混練した後、三本ロール（ＥＸＡＫＴ　Ａｐｐａｒａｔｅｂａｕｓ社製　２２８５１Ｎｏｒｄｅｒｓｔｅｄｔ型）にて、五回パスさせて、実施例１に係る接合材料（ペースト）を得た。実施例１に係る接合材料の配合を表１、２に示す。
　尚、オクタンジオールの沸点は２４４℃であり、引火点は１３５℃である。
〈接合部材の形成〉
　メタルマスク（マスク厚５０μｍｔ）を準備し、銀めっきされた銅基板上にメタルスキージによる手印刷で、実施例１に係る接合材料（ペースト）を印刷法により塗布した。パターンは□５．５ｍｍ、５０μｍ厚とした。
　こうして得られた接合材料が塗布された銅基板を、炉（フリップチップボンダー　Ｍ－９０　ＤＯＮ－４００  ハイソル株式会社製）に設置し、窒素雰囲気（酸素濃度：５００ｐｐｍ以下）中、１００℃１０分間加熱して予備焼成することで、接合材料中における気泡やガス成分を除去した。
　当該予備焼成後、接合材料が塗布された銅基板を２５℃まで冷却し、チップ（□５ｍｍ、厚み０．３ｍｍの銀めっきされたＳｉチップ）を上記塗布面に対してマウントした。
　当該チップがマウントされた銅基板を再び炉中に設置し、１０ＭＰａの加圧を施して、２５０℃まで昇温速度１℃／秒で昇温し、本焼成として２５０℃に達してから５分間保持して、実施例１に係る接合体を得た。
　得られた実施例１に係る接合体の接合力の測定を行った。具体的には、ＪＩＳＺ－０３９１８－５：２００３の「鉛フリーはんだ試験方法　第５部はんだ継ぎ手の引張およびせん断試験方法」に記載のある方法に準じて行った。すなわち、基板上に接合された被接合体（チップ）を水平方向に押し、押される力に耐えかねて接合面が破断するときの力を測定する方法である。本実施例ではＤＡＧＥ社製ボンドテスタ（シリーズ４０００）を使用して試験を行った。シェア高さは５０μｍ、試験速度は５ｍｍ／ｍｉｎ、測定は室温で行った。
　その結果、実施例１に係る接合体における、基板とチップとの間の接合強度（平均シェア強度）は６４．０ＭＰａであった。尚、せん断試験方法は、接合面が破断する際の力（Ｎ）を直接測定しており、接合面積に依存する値である。そこで、測定されたシェア強度を規格化する為、測定された破断する際の力を接合面積（今回の場合は５．０ｍｍ×５．０ｍｍ＝２５．０ｍｍ2）で除した値（単位はＭＰａ）をもって接合強度（平均シェア強度）と定めた。以後の実施例、比較例においても同様である。
　さらに、実施例１に係る接合体の内部におけるボイドの存在率をＸ線測定（Ｘ線透視装置 ＳＭＸ－１６０ＬＴ 島津製作所製）により測定した。具体的には、画像解析ソフトウエアを用いて、ボイドの部分が赤く色づけされるように輝度のレンジ（色のレンジ）を調整し、□５ｍｍの面積を２値化することでボイドの面積比率を計算したものである。当該結果を表１、２に示した。
［実施例２］
　実施例１に係る接合材料の分散媒であるオクタンジオールの添加量を７．９５ｇに変更し、さらに、粘度調整を目的としてＥＸＸＳＯＬ　Ｄ１３０　ＦＬＵＩＤ（エクソンモービル社製）を２．０ｇ添加した以外は、実施例１と同様の製造工程を経て、実施例２に係る接合材料を製造した。そして、実施例１と同様の工程を経て、実施例２に係る接合体を形成し、実施例１と同様の評価を行った。評価結果を表１、２に示す。
［実施例３］
　実施例１に係る接合材料の銀粉を球状銀粒子から、フレーク銀粒子粉末（ＤＯＷＡエレクトロニクス株式会社製ＦＡ－Ｄ－６：平均一次粒子径（Ｄ50）８．３μｍ）へ変更した以外は、実施例１と同様の製造工程を経て、実施例３に係る接合材料を製造した。そして、実施例１と同様の工程を経て、実施例３に係る接合体を形成し、実施例１と同様の評価を行った。評価結果を表１、２に示す。
［実施例４］
　実施例１に係る接合材料のソルビン酸が被覆された銀ナノ粒子凝集体乾燥粉（平均一次粒子径：１００ｎｍ）から、ソルビン酸が被覆された銀ナノ粒子凝集体乾燥粉（平均一次粒子径：６０ｎｍ）へ変更し、フラックスをオキシジ酢酸（和光純薬株式会社製：ジグリコール酸）０．１ｇ、分散媒としてオクタンジオール（協和発酵ケミカル株式会社製：２－エチル－１，３－ヘキサンジオール）の添加量を９．９ｇと変更した以外は、実施例１と同様の製造工程を経て、実施例４に係る接合材料を製造した。そして、実施例１と同様の工程を経て、実施例４に係る接合体を形成し、実施例１と同様の評価を行った。評価結果を表１、２に示す。
［実施例５］
　実施例１に係る接合材料の分散媒であるオクタンジオールの添加量を７．４５ｇに変更し、さらに、粘度調整を目的としてＥＸＸＳＯＬ　Ｄ１３０　ＦＬＵＩＤ（エクソンモービル社製）を２．０ｇ添加し、さらに、粘度調整を目的としてオレイン酸（キシダ化学株式会社製）を０．５ｇ添加した以外は、実施例１と同様の製造工程を経て、実施例５に係る接合材料を製造した。そして、実施例１と同様の工程を経て、実施例５に係る接合体を形成し、実施例１と同様の評価を行った。評価結果を表１、２に示す。
［比較例１］
　実施例１に係る接合材料を準備した。
　そして、チップマウント前の予備焼成を実施せず、接合材料が塗布された銅基板にチップをマウントし、１０ＭＰａの加圧を施して、予備乾燥として１００℃１０分間加熱後、２５０℃まで昇温速度１℃／秒で昇温し、本焼成として２５０℃に達してから５分間保持することで、比較例１に係る接合体を形成し、実施例１と同様の評価を行った。評価結果を表１、２に示す。
［比較例２］
　実施例２に係る接合材料を用い、比較例１と同様の工程を経て、比較例２に係る接合体を形成し、実施例１と同様の評価を行った。評価結果を表１、２に示す。
［比較例３］
　実施例３に係る接合材料を用い、比較例１と同様の工程を経て、比較例３に係る接合体を形成し、実施例１と同様の評価を行った。評価結果を表１、２に示す。
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
［まとめ］
　図１に、実施例１～３および比較例１～３に係る接合体の接合強度を示す。図１は縦軸に接合強度（シェア強度）をとり、横軸に、実施例１－比較例１、実施例２－比較例２、実施例３－比較例３をとった棒グラフである。
　実施例１－比較例１と、実施例２－比較例２と、実施例３－比較例３とは、接合材料として同組成のペーストを用い、実施例１～３においてはチップマウント前の予備焼成を実施し、比較例１～３においてはチップマウント前の予備焼成を実施しなかったものである。
　図１より、チップマウント前の予備焼成を実施した実施例１～３に係る接合体は、予備焼成を実施しなかった比較例１～３に係る接合体より２．３～６．２の接合強度を発揮することが判明した。
産業上の利用分野
　本発明に係る接合材料および接合体、並びに接合方法は、非絶縁型半導体装置、ベアチップ実装組み立て技術への応用、パワーデバイス（ＩＧＢＴ、整流ダイオード、パワートランジスタ、パワーＭＯＳＦＥＴ、絶縁ゲートバイポーラトランジスタ、サイリスタ、ゲートターンオフサイリスタ、トライアックへの適用が可能である。また、表面をクロム処理したガラス上への接合材へも適用可能であり、ＬＥＤを使った照明装置の電極やフレームの接合材へも適用可能である。

Claims (13)

  1. 　複数の被接合部材を接合する接合方法であって、
    　一の被接合部材の接合面へ接合材料を塗布する工程と、
    　接合材料を塗布された一の被接合部材を、所定の温度に加熱する予備焼成工程と、
    　加熱された一の被接合部材に塗布された接合材料の層上へ、二の被接合部材を設置する工程と、
    　二の被接合部材が設置された一の被接合部材を、前記予備焼成工程の温度より高い温度に加熱して、一の被接合部材と二の被接合部材との間に接合層を形成する本焼成工程とを有する接合方法。
  2. 　前記接合材料は、２以上のカルボキシル基を有する有機物質を含有する請求項１に記載の接合方法。
  3. 　前記接合材料は、少なくとも平均一次粒子径が１ｎｍ以上２００ｎｍ以下の銀ナノ粒子を含有する、請求項１または２に記載の接合方法。
  4. 　前記本焼成工程において、一の被接合部材と二の被接合部材との接合面へ２０ＭＰａ以下の加圧を行なう請求項１ないし３のいずれかに記載の接合方法。
  5. 　炭素数８以下の脂肪酸で被覆され平均一次粒子径が１ｎｍ以上２００ｎｍ以下の銀ナノ粒子と、平均粒子径が０．５μｍ以上１０μｍ以下の銀粒子と、２以上のカルボキシル基を有する有機物質と、分散媒とを含む接合材料。
  6. 　前記２以上のカルボキシル基を有する有機物質が、エーテル結合を有する請求項５に記載の接合材料。
  7. 　前記２以上のカルボキシル基を有する有機物質が、オキシジ酢酸である請求項５または６に記載の接合材料。
  8. 　前記銀ナノ粒子が、炭素数３以上６以下の脂肪酸で被覆されている請求項５ないし７のいずれかに記載の接合材料。
  9. 　複数の被接合部材を接合する接合方法であって、
    　一の被接合部材の接合面へ請求項５ないし８のいずれかに記載の接合材料を塗布する工程と、
    　前記接合材料を塗布された一の被接合部材を、所定の温度に加熱する予備焼成工程と、
    　加熱された一の被接合部材に塗布された前記接合材料の層上へ、二の被接合部材を設置する工程と、
    　二の被接合部材が設置された一の被接合部材を、前記予備焼成工程の温度より高い温度に加熱して、一の被接合部材と二の被接合部材との間に接合層を形成する本焼成工程とを有する接合方法。
  10. 　前記本焼成工程を不活性ガス雰囲気下で行う請求項１ないし４、９のいずれかに記載の接合方法。
  11. 　前記本焼成工程を１５０℃以上５００℃以下の温度で行う請求項１ないし４、９または１０のいずれかに記載の接合方法。
  12. 　前記本焼成工程における加熱の昇温速度を、０．１℃／秒以上２．０℃／秒以下で行う請求項１ないし４、９ないし１１のいずれかに記載の接合方法。
  13. 　複数の被接合部材が接合層により接合された接合体であって、当該接合層に存在するボイド率が２．０％以下である接合体。
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