WO2021064826A1 - 接合用銅ペースト、接合体の製造方法及び接合体 - Google Patents

接合用銅ペースト、接合体の製造方法及び接合体 Download PDF

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Publication number
WO2021064826A1
WO2021064826A1 PCT/JP2019/038626 JP2019038626W WO2021064826A1 WO 2021064826 A1 WO2021064826 A1 WO 2021064826A1 JP 2019038626 W JP2019038626 W JP 2019038626W WO 2021064826 A1 WO2021064826 A1 WO 2021064826A1
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Prior art keywords
bonding
copper
copper paste
particles
mass
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PCT/JP2019/038626
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English (en)
French (fr)
Inventor
征央 根岸
偉夫 中子
美智子 名取
大 石川
千絵 須鎌
祐貴 川名
Original Assignee
昭和電工マテリアルズ株式会社
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Application filed by 昭和電工マテリアルズ株式会社 filed Critical 昭和電工マテリアルズ株式会社
Priority to EP19947706.8A priority Critical patent/EP4023367A4/en
Priority to PCT/JP2019/038626 priority patent/WO2021064826A1/ja
Priority to US17/764,273 priority patent/US20220371087A1/en
Priority to JP2021550779A priority patent/JP7392728B2/ja
Priority to CN201980100833.6A priority patent/CN114502301A/zh
Priority to KR1020227012117A priority patent/KR20220073763A/ko
Publication of WO2021064826A1 publication Critical patent/WO2021064826A1/ja

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    • 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
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    • 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
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    • H01L2924/1306—Field-effect transistor [FET]
    • H01L2924/13091—Metal-Oxide-Semiconductor Field-Effect Transistor [MOSFET]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/15—Details of package parts other than the semiconductor or other solid state devices to be connected
    • H01L2924/181—Encapsulation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/30—Technical effects
    • H01L2924/35—Mechanical effects
    • H01L2924/351—Thermal stress
    • H01L2924/3512—Cracking
    • H01L2924/35121—Peeling or delaminating
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/30—Technical effects
    • H01L2924/37—Effects of the manufacturing process
    • H01L2924/37001—Yield

Definitions

  • the present invention relates to a copper paste for bonding, a method for producing a bonded body, and a bonded body.
  • Patent Document 1 discloses a bonding material containing cupric oxide particles having an average particle size of 1 nm to 50 ⁇ m and a reducing agent as a bonding material for bonding a semiconductor element and an electrode.
  • Patent Document 2 discloses copper nanoparticles, copper microparticles, copper submicroparticles, or a bonding material containing both of them.
  • Patent No. 5006081 Japanese Unexamined Patent Publication No. 2014-167145
  • the bonding material is required to have printability suitable for the printing process by an automatic printing machine such as a screen printing machine.
  • a paste in which metal particles are dispersed in a dispersion medium can be improved in printability by blending a dispersion medium such as an organic solvent to reduce the viscosity.
  • a dispersion medium such as an organic solvent
  • the present invention has been made in view of the above circumstances, and a copper paste for bonding capable of improving printability while maintaining sufficient bondability, and a method for producing a bonded body and a bonded body using the same.
  • the purpose is to provide.
  • One aspect of the present invention relates to a bonding copper paste containing metal particles and a dispersion medium, containing copper particles as metal particles, and containing dihydroterpineol as a dispersion medium.
  • the copper paste for bonding can improve printability while maintaining sufficient bonding properties.
  • a bonded body can be efficiently manufactured by a mass production process using an automatic printing machine such as a screen printing machine.
  • the bonding copper paste may have a metal particle content of 85 to 98% by mass based on the total amount of the bonding copper paste. In this case, it becomes easy to secure the bonding strength, and it becomes easy to cope with the increase in the size of the member to be bonded (for example, the size of the semiconductor element).
  • the copper paste for bonding can further contain a compound having a boiling point of 300 ° C. or higher as a dispersion medium.
  • the copper paste for joining is imparted with plasticity and adhesion until immediately before the start of sintering, facilitating joining without pressure.
  • the bonding copper paste may have a viscosity at 25 ° C. of 100 to 200 Pa ⁇ s. In this case, the compatibility with the automatic printing machine is further improved.
  • the content of the copper particles may be 80 to 100% by mass based on the total mass of the metal particles.
  • the copper paste for joining may be used for screen printing.
  • screen printing is also referred to as stencil printing, and means a printing method in which paste is rubbed on a plate having holes (openings).
  • the squeegee, scraper and the like are not particularly limited, and known ones can be appropriately applied.
  • the copper paste for bonding is a flake-shaped copper particle having a volume average particle diameter of 0.12 to 0.8 ⁇ m and a maximum diameter of 2 to 50 ⁇ m and an aspect ratio of 3.0 or more. May contain microcopper particles of. In this case, it is suitable for joining without pressure.
  • no pressure means that the copper paste for joining is only the weight of the member to be joined (that is, it is not subjected to pressure other than the weight of the member), or in addition to the weight thereof, 0. It means a state of receiving a slight pressure of 01 MPa or less.
  • the content of the sub-micro copper particles in the copper paste for bonding is 30 to 90% by mass based on the total mass of the copper particles, and the content of the micro copper particles is based on the total mass of the copper particles. It may be 10 to 70% by mass.
  • the copper paste for joining may be for non-pressurizing joining.
  • Another aspect of the present invention is a method for manufacturing a joined body including a first member, a second member, and a joint portion for joining the first member and the second member.
  • the present invention relates to a method for producing a bonded body, comprising a first step of preparing the laminated body and a second step of sintering a copper paste for bonding the laminated body. According to this manufacturing method, by using the copper paste for bonding, both printability and bondability can be achieved, and a bonded body can be efficiently manufactured.
  • the above printing may be screen printing.
  • the bonding copper paste may be heated without pressure and sintered. In this case, damage to the members joined by the non-pressurized joining can be reduced.
  • At least one of the first member and the second member described above may be a semiconductor element.
  • a semiconductor device can be obtained as a bonded body.
  • Another aspect of the present invention includes a first member, a second member, and a joint portion for joining the first member and the second member, and the joint portion is a sintering of the copper paste for joining.
  • At least one of the first member and the second member described above may be a semiconductor element. That is, the junction may be a semiconductor device.
  • the present invention it is possible to provide a copper paste for bonding capable of improving printability while maintaining sufficient bondability, and a method for producing a bonded body using the copper paste and a bonded body.
  • the bonding copper paste of the present embodiment contains metal particles and a dispersion medium, contains copper particles as metal particles, and contains dihydroterpineol as a dispersion medium.
  • a set of a plurality of copper particles is also referred to as "copper particles”. The same applies to metal particles other than copper particles.
  • Copper particles examples of the copper particles include sub-micro copper particles, micro copper particles, and copper particles other than these.
  • the submicro copper particles are copper particles having a particle size of 0.01 ⁇ m or more and less than 1.00 ⁇ m.
  • the submicro copper particles preferably have sinterability in a temperature range of 150 ° C. or higher and 300 ° C. or lower.
  • the submicro copper particles preferably contain copper particles having a particle size of 0.01 to 0.80 ⁇ m.
  • the sub-micro copper particles may contain 10% by mass or more of copper particles having a particle size of 0.01 to 0.80 ⁇ m, may contain 20% by mass or more, may contain 30% by mass or more, and may contain 100% or more. It may contain mass%.
  • the particle size of the copper particles can be calculated from, for example, an SEM image.
  • the powder of copper particles is placed on a carbon tape for SEM with a spatula to prepare a sample for SEM.
  • This SEM sample is observed with an SEM device at a magnification of 5000.
  • a quadrangle circumscribing the copper particles of this SEM image is drawn by image processing software, and one side thereof is used as the particle size of the particles.
  • the volume average particle size of the sub-micro copper particles is preferably 0.01 to 0.80 ⁇ m.
  • the volume average particle size of the sub-micro copper particles is 0.01 ⁇ m or more, the effects of suppressing the synthesis cost of the sub-micro copper particles, good dispersibility, and suppressing the amount of the surface treatment agent used can be easily obtained.
  • the volume average particle size of the sub-micro copper particles is 0.80 ⁇ m or less, the effect of excellent sinterability of the sub-micro copper particles can be easily obtained.
  • the volume average particle diameter of the submicro copper particles is 0.02 ⁇ m or more, 0.05 ⁇ m or more, 0.10 ⁇ m or more, 0.11 ⁇ m or more, 0.12 ⁇ m or more, 0.15 ⁇ m. As mentioned above, it may be 0.2 ⁇ m or more or 0.3 ⁇ m or more. Further, from the viewpoint that the above effect is further exhibited, the volume average particle diameter of the submicro copper particles may be 0.60 ⁇ m or less, 0.50 ⁇ m or less, 0.45 ⁇ m or less, or 0.40 ⁇ m or less.
  • the volume average particle diameter of the submicro copper particles is, for example, 0.01 to 0.60 ⁇ m, 0.01 to 0.50 ⁇ m, 0.02 to 0.80 ⁇ m, 0.05 to 0.80 ⁇ m, 0.10 to 0. .80 ⁇ m, 0.11 to 0.80 ⁇ m, 0.12 to 0.80 ⁇ m, 0.15 to 0.80 ⁇ m, 0.15 to 0.60 ⁇ m, 0.20 to 0.50 ⁇ m, 0.30 to 0.45 ⁇ m Or, it may be 0.30 to 0.40 ⁇ m.
  • the volume average particle diameter means a 50% volume average particle diameter.
  • the volume average particle diameter of the metal particles can be measured by, for example, the following method. First, the metal particles as a raw material or the dry metal particles obtained by removing the volatile components from the metal paste are dispersed in a dispersion medium using a dispersant. Next, the volume average particle size of the obtained dispersion is measured with a light scattering method particle size distribution measuring device (for example, Shimadzu nanoparticle size distribution measuring device (SALD-7500 nano, manufactured by Shimadzu Corporation)).
  • SALD-7500 nano Shimadzu nanoparticle size distribution measuring device
  • the shape of the sub-micro copper particles is not particularly limited.
  • Examples of the shape of the submicro copper particles include spherical, massive, needle-like, columnar, flake-like, substantially spherical, and aggregates thereof.
  • the shape of the sub-microcopper particles may be spherical, substantially spherical or flake-shaped, and flammable, dispersible, flake-shaped microparticles (for example, flake-shaped microcopper particles). From the viewpoint of mixing with and the like, it may be spherical or substantially spherical.
  • the term "flake-like" includes a plate-like shape such as a plate-like shape or a scaly shape.
  • the aspect ratio of the sub-microcopper particles may be 5.0 or less from the viewpoint of dispersibility, filling property, and mixing property with flake-shaped microparticles (for example, flake-shaped microcopper particles). It may be 0 or less, 2.5 or less, or 2.0 or less.
  • the "aspect ratio" indicates "the long side of the particle / the thickness of the particle". The long side of the particle and the thickness of the particle can be obtained from, for example, an SEM image of the particle.
  • the sub-micro copper particles may be treated with a surface treatment agent from the viewpoint of dispersibility of the sub-micro copper particles.
  • the surface treatment agent may be adsorbed on the surface of the sub-micro copper particles by hydrogen bonds or the like, or may react with the sub-micro copper particles and be bonded to the surface of the sub-micro copper particles. That is, the submicrocopper particles may have a compound derived from a specific surface treatment agent.
  • the surface treatment agent is included in the organic compound contained in the copper paste for bonding.
  • Examples of the surface treatment agent include organic acids having 2 to 18 carbon atoms.
  • Examples of organic acids having 2 to 18 carbon atoms include acetic acid, propanoic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanic acid, caprylic acid, methylheptanic acid, ethylhexanoic acid, propylpentanoic acid, pelargonic acid and methyloctane.
  • Acid ethylheptanic acid, propylhexanoic acid, caprylic acid, methylnonanoic acid, ethyloctanoic acid, propylheptanic acid, butylhexanoic acid, undecanoic acid, methyldecanoic acid, ethylnonanoic acid, propyloctanoic acid, butylheptanic acid, lauric acid, methylundecane Acids, ethyldecanoic acid, propylnonanoic acid, butyloctanoic acid, pentylheptanic acid, tridecanoic acid, methyldodecanoic acid, ethylundecanoic acid, propyldecanoic acid, butylnonanoic acid, pentyloctanoic acid, myristic acid, methyltridecanoic acid, ethyldodecanoic acid , Caprylic acid
  • organic acid one kind may be used alone, or two or more kinds may be used in combination.
  • organic acid By combining such an organic acid with the above-mentioned sub-micro copper particles, there is a tendency that both the dispersibility of the sub-micro copper particles and the desorption of the organic acid at the time of sintering can be achieved at the same time.
  • the treatment amount of the surface treatment agent is 0.07 to 2.10% by mass and 0.10 to 1.1 by mass based on the total mass of the submicro copper particles after the surface treatment from the viewpoint of the dispersibility of the submicro copper particles. It may be 60% by mass or 0.20 to 1.10% by mass.
  • the treatment amount of the surface treatment agent may be 0.07% by mass or more, 0.10% by mass or more, or 0.20% by mass or more based on the total mass of the sub-micro copper particles after the surface treatment.
  • the treatment amount of the surface treatment agent may be 2.10% by mass or less, 1.60% by mass or less, or 1.10% by mass or less based on the total mass of the sub-micro copper particles after the surface treatment.
  • the treatment amount of the surface treatment agent may be an amount that adheres to the surface of the sub-micro copper particles in a single-layer to a triple-layer.
  • This processing amount is measured by the following method.
  • sub-micro copper particles commercially available ones can be used.
  • examples of commercially available materials containing sub-micro copper particles include CH-0200 (manufactured by Mitsui Metal Mining Co., Ltd., volume average particle size 0.36 ⁇ m) and HT-14 (manufactured by Mitsui Metal Mining Co., Ltd., volume average grain size).
  • the content of the sub-micro copper particles may be 30% by mass or more, 35% by mass or more, 40% by mass or more, or 50% by mass or more, based on the total mass of the copper particles contained in the bonding copper paste, 90% by mass or more. It may be 0% by mass or less or 85% by mass or less.
  • the content of the sub-micro copper particles is 30 to 90% by mass, 35 to 90% by mass, 40 to 85% by mass, or 50 to 85% by mass based on the total mass of the copper particles contained in the bonding copper paste. May be.
  • the content of the sub-micro copper particles is within the above range, it becomes easy to secure the bonding strength of the bonded body produced by sintering the bonding copper paste.
  • the bonding copper paste is used for bonding microdevices, the microdevices tend to exhibit good die shear strength and connection reliability.
  • the micro copper particles are copper particles having a particle size of 1 ⁇ m or more and less than 50 ⁇ m.
  • the micro copper particles preferably contain copper particles having a particle size of 2.0 to 50 ⁇ m.
  • the micro copper particles may contain 50% by mass or more of copper particles having a particle size of 2.0 to 50 ⁇ m, 70% by mass or more, 80% by mass or more, or 100% by mass. You may be.
  • the volume average particle size of the micro copper particles is preferably 2.0 to 50 ⁇ m.
  • the volume average particle diameter of the micro copper particles may be 2.0 to 20 ⁇ m, 2.0 to 10 ⁇ m, 3.0 to 20 ⁇ m, or 3.0 to 10 ⁇ m.
  • the volume average particle size of the microcopper particles may be 2.0 ⁇ m or more or 3.0 ⁇ m or more.
  • the volume average particle size of the microcopper particles may be 50 ⁇ m or less, 20 ⁇ m or less, or 10 ⁇ m or less.
  • the shape of the micro copper particles is not particularly limited.
  • Examples of the shape of the microcopper particles include a spherical shape, a lump shape, a needle shape, a flake shape, a substantially spherical shape, and an aggregate thereof.
  • the preferred shape of the microcopper particles is flake-like.
  • the micro-copper particles may contain flake-shaped micro-copper particles in an amount of 50% by mass or more, 70% by mass or more, 80% by mass or more, or 100% by mass.
  • the micro copper particles in the bonding copper paste are oriented substantially parallel to the bonding surface, and the direction of the bonding surface when the bonding copper paste is sintered Volume shrinkage can be suppressed, and it becomes easy to secure the bonding strength of the bonded body produced by sintering the bonding copper paste.
  • the bonding copper paste is used for bonding microdevices, the microdevices tend to exhibit good die shear strength and connection reliability.
  • the aspect ratio of the flake-shaped microcopper particles is preferably 3.0 or more, more preferably 4.0 or more, still more preferably 6.0 or more. ..
  • the maximum diameter and the average maximum diameter of the flake-shaped microcopper particles may be 2.0 to 50 ⁇ m, 3.0 to 50 ⁇ m, or 3.0 to 20 ⁇ m.
  • the maximum diameter and the average maximum diameter of the flake-shaped microcopper particles can be obtained from, for example, an SEM image of the particles.
  • the maximum diameter and the average maximum diameter of the flake-shaped microcopper particles are obtained as, for example, the major axis X and the average value Xav of the major axis of the flake-shaped microcopper particles.
  • the major axis X is a parallel two plane selected so that the distance between the two parallel planes circumscribing the flake-shaped micro copper particles is maximized in the three-dimensional shape of the flake-shaped micro copper particles. The distance.
  • the presence or absence of treatment with a surface treatment agent is not particularly limited.
  • the microcopper particles may be treated with a surface treatment agent. That is, the microcopper particles may have a compound derived from the surface treatment agent.
  • the surface treatment agent may be adsorbed on the surface of the microcopper particles by hydrogen bonds or the like, or may react with the microcopper particles and be bonded to the surface of the microcopper particles.
  • the surface treatment agent may be one that is removed by heating at the time of joining.
  • Examples of such surface treatment agents include aliphatic carboxylic acids such as dodecanoic acid, palmitic acid, heptadecanoic acid, stearic acid, arachidic acid, linoleic acid, linoleic acid, and oleic acid; terephthalic acid, pyromellitic acid, o-.
  • Aromatic carboxylic acids such as phenoxybenzoic acid; fatty alcohols such as cetyl alcohol, stearyl alcohol, isobornylcyclohexanol, tetraethylene glycol; aromatic alcohols such as p-phenylphenol; octylamine, dodecylamine, stearylamine, etc. Alkylamine; aliphatic nitriles such as stearonitrile and decanenitrile; silane coupling agents such as alkylalkoxysilane; polymer-treated materials such as polyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone, and silicone oligomers.
  • the surface treatment agent one type may be used alone, or two or more types may be used in combination.
  • micro copper particles commercially available ones can be used.
  • examples of commercially available materials containing micro copper particles include 1050YF (manufactured by Mitsui Metal Mining Co., Ltd., volume average particle size 1.7 ⁇ m) and MA-C025KFD (manufactured by Mitsui Metal Mining Co., Ltd., volume average particle size 7.
  • 3L3 manufactured by Fukuda Metal Foil Powder Industry Co., Ltd., volume average particle size 8.0 ⁇ m
  • 2L3N manufactured by Fukuda Metal Foil Powder Industry Co., Ltd., volume average particle size 9.9 ⁇ m
  • 3L3N (Fukuda Metal Foil Powder Industry Co., Ltd.) Examples thereof include a volume average particle diameter of 7 ⁇ m manufactured by Mitsui Kinzoku Mining Co., Ltd. and a volume average particle diameter of 3.8 ⁇ m manufactured by Mitsui Metal Mining Co., Ltd.
  • the content of the micro copper particles may be 10% by mass or more, 15% by mass or more, or 20% by mass or more, and 70% by mass or less, 50% by mass, based on the total mass of the copper particles contained in the bonding copper paste. % Or less, 45% by mass or less, or 40% by mass or less.
  • the content of the micro copper particles is 10 to 70% by mass, 10 to 65% by mass, 10 to 50% by mass, 15 to 60% by mass, based on the total mass of the copper particles contained in the bonding copper paste. It may be 15 to 50% by mass, or 15 to 45% by mass.
  • the content of the micro copper particles is within the above range, peeling of the joint portion (for example, a sintered body), generation of voids and cracks can be suppressed, and the joint strength can be ensured.
  • the bonding copper paste is used for bonding microdevices, the microdevices tend to exhibit good die shear strength and connection reliability.
  • the content of the flake-shaped micro-copper particles may be the same as the above-mentioned range of the content of the micro-copper particles. When the content of the flake-shaped microcopper particles is in such a range, the above effect tends to be further exerted.
  • Examples of copper particles other than sub-micro copper particles and micro copper particles include copper nanoparticles.
  • Copper nanoparticles refer to copper particles having a particle size of less than 0.01 ⁇ m.
  • the surface of copper nanoparticles is generally coated with a carboxylic acid or amine (called a surface coating material). Copper nanoparticles have a larger specific surface area than copper microparticles, and the proportion of surface coating material per unit mass tends to increase. Therefore, since a large amount of surface coating material is desorbed during sintering (heating), the volume shrinkage during sintering tends to increase as compared with copper microparticles.
  • the content of the copper nanoparticles is preferably 10% by mass or less, more preferably 5% by mass or less, and further preferably not contained, based on the total mass of the copper particles.
  • the content of the copper particles in the bonding copper paste of the present embodiment may be 80 to 100% by mass, or 90 to 100% by mass, based on the total mass of the metal particles contained in the bonding copper paste. It may be 95 to 100% by mass.
  • the bonding copper paste of the present embodiment contains sub-micro copper particles and micro-copper particles.
  • the sub-micro copper particles and the micro copper particles are used in combination, volume shrinkage and sintering shrinkage due to drying are likely to be suppressed, and the copper paste for bonding is less likely to peel off from the bonding surface during sintering. That is, by using the sub-micro copper particles and the micro copper particles in combination, the volume shrinkage when the copper paste for bonding is sintered is suppressed, and the bonded body can have more sufficient bonding strength.
  • the micro device tends to exhibit better die shear strength and connection reliability.
  • the total content of the sub-micro copper particles and the content of the micro copper particles may be 80 to 100% by mass based on the total mass of the metal particles contained in the bonding copper paste.
  • the total content of the sub-micro copper particles and the content of the micro copper particles is within the above range, the volume shrinkage when the bonding copper paste is sintered can be sufficiently reduced, and the bonding copper paste is sintered. It becomes easy to secure the bonding strength of the bonded body produced in the above.
  • the bonding copper paste is used for bonding microdevices, the microdevices tend to exhibit good die shear strength and connection reliability.
  • the total content of the sub-micro copper particles and the content of the micro copper particles may be 90% by mass or more, based on the total mass of the metal particles, and may be 95% by mass. It may be the above, or may be 100% by mass.
  • the bonding copper paste of the present embodiment has submicro copper particles having a volume average particle diameter of 0.12 to 0.8 ⁇ m and flakes having a maximum diameter of 2 to 50 ⁇ m and an aspect ratio of 3.0 or more. May contain microcopper particles of. In this case, it is suitable for joining without pressure.
  • the content of the sub-micro copper particles in the bonding copper paste is 30 to 90% by mass based on the total mass of the copper particles, and the content of the micro copper particles is the total mass of the copper particles. As a reference, it may be 10 to 70% by mass.
  • the bonding copper paste of the present embodiment may contain metal particles other than copper particles (also referred to as "other metal particles").
  • Examples of other metal particles include particles such as zinc, nickel, silver, gold, palladium, and platinum.
  • the volume average particle diameter of the other metal particles may be 0.01 to 10 ⁇ m, 0.01 to 5 ⁇ m, or 0.05 to 3 ⁇ m.
  • the shapes of the other metal particles are not particularly limited.
  • the content of the other metal particles may be less than 20% by mass and 10% by mass or less based on the total mass of the metal particles contained in the bonding copper paste from the viewpoint of obtaining sufficient bondability. It may be 5% by mass or less, 1% by mass or less, or 0% by mass.
  • the content of the metal particles in the bonding copper paste of the present embodiment may be 85 to 98% by mass, 85 to 95% by mass, or 85 to 90% based on the total amount of the bonding copper paste. It may be mass%, or may be 87-89 mass%.
  • the dispersion medium is not particularly limited as long as it has a function of dispersing metal particles, and may be volatile.
  • volatile dispersion medium include alcohols such as monohydric alcohols and polyhydric alcohols, ethers, esters, acid amides, aliphatic hydrocarbons, aromatic hydrocarbons and the like. Specifically, alcohols such as cyclohexanol, ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, ⁇ -terpineol ( ⁇ -terpineol), dihydroterpineol (dihydroterpineol); diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol.
  • Dibutyl ether diethylene glycol butyl methyl ether, diethylene glycol isopropyl methyl ether, triethylene glycol dimethyl ether, triethylene glycol butyl methyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dibutyl ether, propylene glycol dipropyl ether, tripropylene glycol dimethyl ether, etc.
  • esters such as ethylene glycol ethyl ether acetate, ethylene glycol butyl ether acetate, diethylene glycol ethyl ether acetate, diethylene glycol butyl ether acetate, dipropylene glycol methyl ether acetate (DPMA), ethyl lactate, butyl lactate, ⁇ -butyrolactone, propylene carbonate, etc.
  • Acid amides such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide; aliphatic hydrocarbons such as cyclohexane, octane, nonane, decane, undecane; benzene, toluene, xylene, etc. Examples include aromatic hydrocarbons.
  • the copper paste for bonding of the present embodiment contains dihydroterpineol as a dispersion medium from the viewpoint of achieving both printability and bonding property.
  • the content of the dispersion medium may be 2% by mass or more, 5% by mass or more or 10% by mass or more, based on the total mass of the bonding copper paste, and is 50% by mass or less, 30% by mass or less, 20% by mass. It may be less than or equal to 15% by mass or less.
  • the content of the dispersion medium may be 2 to 50% by mass, 5 to 30% by mass, or 5 to 20% by mass based on the total mass of the bonding copper paste.
  • the content of the dispersion medium may be 2 to 50 parts by mass, may be 5 to 50 parts by mass, and 2 to 15 parts by mass, with the total mass of the metal particles contained in the bonding copper paste as 100 parts by mass.
  • the bonding copper paste can be adjusted to a more appropriate viscosity, and the sintering of copper particles is less likely to be hindered.
  • the content of dihydroterpineol in the bonding copper paste of the present embodiment may be 50 to 100% by mass, 50 to 90% by mass, or 60 to 80% based on the total mass of the dispersion medium. It may be 100% by mass or 100% by mass.
  • the bonding copper paste preferably contains a compound having a boiling point of 300 ° C. or higher (hereinafter, may be referred to as a high boiling point dispersion medium) as a dispersion medium.
  • a high boiling point dispersion medium By including the high boiling point dispersion medium, the copper paste for bonding is imparted with plasticity and adhesion until immediately before the start of sintering, and bonding without pressure is facilitated.
  • the boiling point of the high boiling point dispersion medium is 300 to 450 ° C. from the viewpoint that it does not interfere with sintering and densification when the copper paste for bonding is sintered and is quickly evaporated and removed when the bonding temperature is reached. It may be 305 to 400 ° C., or 310 to 380 ° C.
  • the boiling point refers to the temperature under atmospheric pressure (1 atm). ..
  • a dispersion medium having a boiling point of less than 300 ° C. may be referred to as a low boiling point dispersion
  • High boiling point dispersion media include isobornylcyclohexanol (MTPH, manufactured by Nippon Terpen Chemical Co., Ltd.), butyl stearate, Exepearl BS (manufactured by Kao Co., Ltd.), stearyl stearate, Exepearl SS (manufactured by Kao Co., Ltd.), stearer.
  • MTPH isobornylcyclohexanol
  • BS manufactured by Nippon Terpen Chemical Co., Ltd.
  • stearyl stearate manufactured by Kao Co., Ltd.
  • stearer manufactured by Kao Co., Ltd.
  • the high boiling point dispersion medium contains at least one selected from the group consisting of isobornylcyclohexanol, tributyrin, butyl stearate and octyl octanate. ..
  • the content of the high boiling point dispersion medium may be 2% by mass or more, 2.2% by mass or more or 2.4% by mass or more, and 50% by mass or less, 45% by mass, based on the total mass of the bonding copper paste. % Or less, 40% by mass or less, 20% by mass or less, 10% by mass or less, or 5% by mass or less.
  • the content of the compound having a boiling point of 300 ° C. or higher may be 2 to 50% by mass, 2 to 20% by mass, or 2 to 5% by mass, based on the total mass of the copper paste for bonding. May be%.
  • the content of the high boiling point dispersion medium may be 10 to 50% by mass, 20 to 40% by mass, or 25 to 35% by mass based on the total mass of the dispersion medium. ..
  • the bonding copper paste is an additive such as a nonionic surfactant, a fluorine-based surfactant and other wetting improver; a surface tension adjuster; a dispersant such as an alkylamine and an alkylcarboxylic acid; and a defoaming agent such as silicone oil.
  • An ion trapping agent such as an inorganic ion exchanger; a saturated higher alcohol or the like can be contained.
  • the content of the additive can be appropriately adjusted as long as the effect of the present invention is not impaired.
  • the viscosity of the copper paste for bonding described above is not particularly limited, but the viscosity at 25 ° C. may be 100 to 250 Pa ⁇ s from the viewpoint of conformity with methods such as screen printing, particularly printing conditions of an automatic printing machine. It may be 100 to 200 Pa ⁇ s, and may be 100 to 170 Pa ⁇ s.
  • the viscosity of the bonding copper paste can be measured based on the solder paste viscosity measuring method (JIS Z 3284-1: 2014) standardized by JIS, and the above viscosity can be measured with the viscometer TV-33 (Toki Sangyo). (Product name, manufactured by Co., Ltd.) and the value when measured using an SPP rotor as a measuring tool under the conditions of a rotation speed of 2.5 rpm and a measurement time of 144 seconds are shown.
  • JIS Z 3284-1: 2014 solder paste viscosity measuring method
  • TV-33 Toki Sangyo
  • the bonding copper paste of the present embodiment printability can be improved while maintaining sufficient bonding properties. Therefore, according to the copper paste for bonding of the present embodiment, the bonded body can be efficiently manufactured by a mass production process using an automatic printing machine such as a screen printing machine. Further, the bonding copper paste of the present embodiment may be used for non-pressurizing bonding.
  • the copper paste for bonding can be prepared by mixing the above-mentioned copper particles, a dispersion medium, and other metal particles and additives contained in some cases. After mixing each component, stirring treatment may be performed.
  • the maximum particle size of the dispersion liquid may be adjusted by a classification operation. At this time, the maximum particle size of the dispersion liquid can be 20 ⁇ m or less, and can be 10 ⁇ m or less.
  • the metal particles such as the sub-micro copper particles, those treated with a surface treatment agent may be used.
  • the bonding copper paste may be prepared by, for example, the following method. First, a dispersant is added to the dispersion medium as needed, and then the submicrocopper particles are mixed and the dispersion treatment is performed. Next, microcopper particles and, if necessary, other metal particles are added to carry out a dispersion treatment.
  • the dispersion method and dispersion conditions suitable for dispersion may differ between the sub-micro copper particles and the micro copper particles. In general, sub-micro copper particles are more difficult to disperse than micro-copper particles, and in order to disperse the sub-micro-copper particles, a strength higher than the strength applied when the micro-copper particles are dispersed is required.
  • the microcopper particles are not only easy to disperse, but may be deformed when high strength is applied to disperse them. Therefore, by performing the procedure as described above, good dispersibility can be easily obtained, and the performance of the bonding copper paste can be further improved.
  • the dispersion treatment can be performed using a disperser or a stirrer.
  • Dispersers and stirrers include, for example, Ishikawa stirrer, Silberson stirrer, cavitation stirrer, rotation / revolution type stirrer, ultra-thin high-speed rotary disperser, ultrasonic disperser, Raikai machine, twin-screw kneader, bead mill, ball mill. , Three-roll mill, homomixer, planetary mixer, ultra-high pressure type disperser and thin layer shear disperser.
  • the classification operation can be performed by, for example, filtration, natural sedimentation and centrifugation.
  • the filter for filtration include a water comb, a metal mesh, a metal filter and a nylon mesh.
  • the stirring process can be performed using a stirrer.
  • the stirrer include an Ishikawa type stirrer, a rotation / revolution type stirrer, a Raikai machine, a twin-screw kneader, a three-roll mill and a planetary mixer.
  • the method for manufacturing a joined body of the present embodiment is a method for manufacturing a joined body including a first member, a second member, and a joint portion for joining the first member and the second member.
  • the bonding copper paste of the present embodiment is printed on at least one bonding surface of the first member and the second member, and the first member, the bonding copper paste, and the second member are laminated in this order. It includes a first step of preparing a laminated body having a laminated structure and a second step of sintering a copper paste for joining the laminated body.
  • first member and the second member include semiconductor elements such as IGBTs, diodes, Schottky barrier diodes, MOS-FETs, thyristors, logics, sensors, analog integrated circuits, LEDs, semiconductor lasers, and transmitters; leads. Frame; Ceramic substrate with metal plate attached (for example, DBC); Base material for mounting semiconductor elements such as LED packages; Metal wiring such as copper ribbon and metal frame; Block body such as metal block; Power supply member such as terminals; Heat dissipation plate; Examples include a water cooling plate.
  • semiconductor elements such as IGBTs, diodes, Schottky barrier diodes, MOS-FETs, thyristors, logics, sensors, analog integrated circuits, LEDs, semiconductor lasers, and transmitters
  • leads Frame
  • Ceramic substrate with metal plate attached for example, DBC
  • Base material for mounting semiconductor elements such as LED packages
  • Metal wiring such as copper ribbon and metal frame
  • Block body such as metal block
  • Power supply member such as terminals
  • the surface of the first member and the second member in contact with the sintered body of the copper paste for joining may contain metal.
  • the metal include copper, nickel, silver, gold, palladium, platinum, lead, tin, cobalt and the like.
  • the metal one type may be used alone, or two or more types may be used in combination.
  • the surface in contact with the sintered body may be an alloy containing the above metal.
  • the metal used for the alloy include zinc, manganese, aluminum, beryllium, titanium, chromium, iron, molybdenum and the like in addition to the above metals.
  • a member having various metal plating chip having metal plating, lead frame having various metal plating, etc.
  • a wire, a heat spreader, and a metal plate are attached.
  • Examples thereof include a ceramic substrate, a lead frame made of various metals, a copper plate, and a copper foil.
  • Examples of the method for printing the bonding copper paste of the present embodiment on the bonding surface of the member include screen printing (stencil printing), transfer printing, offset printing, letterpress printing, recess printing, gravure printing, stencil printing, jet printing, and the like. Will be printed.
  • a method using a dispenser for example, a jet dispenser, a needle dispenser
  • a method by soft lithography, particle deposition may be used.
  • the thickness of the bonding copper paste may be 1 ⁇ m or more, 5 ⁇ m or more, 10 ⁇ m or more, 15 ⁇ m or more, 20 ⁇ m or more or 50 ⁇ m or more, and is 3000 ⁇ m or less, 1000 ⁇ m or less, 500 ⁇ m or less, 300 ⁇ m or less, 250 ⁇ m or less or 150 ⁇ m or less. You can do it.
  • the thickness of the bonding copper paste may be 1 to 1000 ⁇ m, 10 to 500 ⁇ m, 50 to 200 ⁇ m, 10 to 3000 ⁇ m, or 15 to 500 ⁇ m. It may be 20 to 300 ⁇ m, 5 to 500 ⁇ m, 10 to 250 ⁇ m, or 15 to 150 ⁇ m.
  • the copper paste for bonding of the present embodiment can be printed by screen printing, and it is possible to improve the printing speed, expand the area of the mask opening, and the like.
  • the opening area of the mask may be, for example, 4 mm 2 or more, 9 mm 2 or more, 25 mm 2 or more, 49 mm 2 or more, 100 mm 2 or more. May be good.
  • FIG. 1 is a schematic diagram for explaining screen printing.
  • the bonding copper of the present embodiment is shown on the first member 30 arranged on the stage 35 by using the mask 32 and the screen printing machine provided with the squeegee 36.
  • a series of processes when printing the paste 34 is shown. In this process, two squeegees are used for reciprocating printing. First, the paste 34 is supplied to one end of the mask 32 ((a) in FIG. 1). Next, one of the squeegees 36 is pressed against the mask 32 with a predetermined printing pressure and moved in one direction to print (coat) the paste 34 on the opening of the mask 32 ((b) in FIG. 1).
  • the paste may be supplied to the end of the coat.
  • the paste 34 is printed (printed) by moving the other squeegee 36 in the opposite direction while pressing the other squeegee 36 at the end position of the coat with a predetermined printing pressure (FIG. 1 (c)).
  • the first member 30 is removed from the mask 32, and printing is completed ((d) in FIG. 1.
  • the bonding copper paste 38 having a predetermined shape is printed on the first member 30.
  • the printing pressure can be, for example, 0.01 to 0.3 MPa.
  • the printing speed can be adjusted, for example, in the range of 15 to 300 mm / s.
  • the paste is filled in the opening of the mask with the scraper, and the paste filled with the squeegee is transferred onto the member for printing. Good.
  • the copper paste for joining printed on the member may be appropriately dried from the viewpoint of suppressing flow and generation of voids during sintering.
  • the gas atmosphere at the time of drying may be in the atmosphere, in an oxygen-free atmosphere such as nitrogen or rare gas, or in a reducing atmosphere such as hydrogen or formic acid.
  • the drying method may be drying by leaving at room temperature (for example, 10 to 30 ° C.), heating drying, or vacuum drying.
  • heat drying or vacuum drying for example, a hot plate, a hot air dryer, a hot air heating furnace, a nitrogen dryer, an infrared dryer, an infrared heating furnace, a far infrared heating furnace, a microwave heating device, a laser heating device, an electromagnetic wave.
  • a heating device a heater heating device, a steam heating furnace, a hot plate pressing device, or the like can be used.
  • the drying temperature and time may be appropriately adjusted according to the type and amount of the volatile components used (for example, monohydric aliphatic alcohol and solvent component).
  • the drying conditions may be, for example, conditions for drying at 50 to 180 ° C. for 1 to 120 minutes.
  • the laminate can be obtained by arranging one member on the other member.
  • Specific methods for example, a method of arranging the first member on the second member on which the copper paste for joining is printed
  • the copper paste for bonding can be sintered by heat-treating the laminate.
  • a sintered body to be a joint can be obtained.
  • heat treatment for example, a hot plate, a hot air dryer, a hot air heating furnace, a nitrogen dryer, an infrared dryer, an infrared heating furnace, a far infrared heating furnace, a microwave heating device, a laser heating device, an electromagnetic heating device, etc.
  • a heater heating device, a steam heating furnace, or the like can be used.
  • the gas atmosphere at the time of sintering may be an oxygen-free atmosphere from the viewpoint of suppressing oxidation of the sintered body and the members (for example, the first member and the second member).
  • the gas atmosphere at the time of sintering may be a reducing atmosphere from the viewpoint of removing surface oxides of copper particles in the copper paste for bonding.
  • the anoxic atmosphere include an anoxic gas atmosphere such as nitrogen and a rare gas, or a vacuum.
  • Examples of the reducing atmosphere include a pure hydrogen gas atmosphere, a mixed gas atmosphere of hydrogen and nitrogen typified by forming gas, a nitrogen atmosphere containing formic acid gas, a mixed gas atmosphere of hydrogen and rare gas, a rare gas atmosphere containing formic acid gas, and the like. Can be mentioned.
  • the temperature during the heat treatment (for example, the maximum temperature reached) is 170 ° C. or higher and 190 ° C. from the viewpoint of reducing thermal damage to the members (for example, the first member and the second member) and improving the yield. It may be more than or equal to 200 ° C. or higher, and may be 250 ° C. or lower, lower than 250 ° C., 225 ° C. or lower, or lower than 225 ° C.
  • the maximum temperature reached may be 170 to 250 ° C., 170 ° C. or higher and lower than 250 ° C., 190 to 225 ° C., or 190 ° C. or higher and lower than 225 ° C. , 200 to 225 ° C., and may be 200 ° C. or higher and lower than 225 ° C.
  • the bonding copper paste may be heated without pressure and sintered. That is, a state in which only the weight of the member (for example, the first member) laminated on the copper paste for bonding is applied, or in addition to the weight of the laminated member, a pressure of 0.01 MPa or less, preferably 0.005 MPa or less is applied.
  • the laminate can be sintered with, and even in such a case, sufficient bonding strength can be obtained.
  • the pressure received during sintering is within the above range, void reduction, die shear strength and connection reliability can be further improved without impairing the yield because a special pressurizing device is not required.
  • Examples of the method in which the bonding copper paste receives a pressure of 0.01 MPa or less include a method in which a weight is placed on a member (for example, a first member) arranged on the upper side in the vertical direction.
  • FIG. 2 is a schematic cross-sectional view showing an example of a bonded body manufactured by using the bonding copper paste of the present embodiment.
  • the joint body 100 shown in FIG. 2 includes a first member 2, a second member 3, and a joint portion 1 for joining the first member 2 and the second member 3, and the joint portion 1 is described above. It consists of a sintered body of copper paste for joining.
  • the above-mentioned ones can be mentioned.
  • a bonded body having sufficient bonding strength can be efficiently produced even by a mass production process using an automatic printing machine such as a screen printing machine.
  • the die shear strength of the bonded body 100 may be 15 MPa or more, 20 MPa or more, or 25 MPa or more from the viewpoint of sufficiently joining the first member 2 and the second member 3. It may be 30 MPa or more.
  • the die-share strength can be measured using a universal bond tester (Royce 650, manufactured by Royce Instruments), a universal bond tester (4000 series, manufactured by DAGE), or the like.
  • the thermal conductivity of the sintered body 1 of the copper paste for bonding may be 100 W / (m ⁇ K) or more, and 120 W / (m ⁇ K) or more from the viewpoint of heat dissipation and connection reliability at high temperatures. It may be 150 W / (m ⁇ K) or more.
  • the thermal conductivity can be calculated from the thermal diffusivity, specific heat capacity, and density of the sintered body of the copper paste for bonding.
  • the joint body 100 when the first member 2 is a semiconductor element, the joint body 100 is a semiconductor device.
  • the obtained semiconductor device can have sufficient die shear strength and connection reliability.
  • FIG. 3 is a schematic cross-sectional view showing an example of a semiconductor device manufactured by using the bonding copper paste of the present embodiment.
  • the semiconductor device 110 shown in FIG. 3 is on the lead frame 15a via the sintered body 11, the lead frame 15a, the lead frame 15b, the wire 16, and the sintered body 11 of the copper paste for bonding according to the present embodiment.
  • a semiconductor element 18 connected to the above and a mold resin 17 for molding the semiconductor elements 18 are provided.
  • the semiconductor element 18 is connected to the lead frame 15b via the wire 16.
  • Examples of the semiconductor device according to the present embodiment include power modules such as diodes, rectifiers, thyristors, MOS gate drivers, power switches, power MOSFETs, IGBTs, shotkey diodes, and fast recovery diodes; transmitters; amplifiers; high-brightness LEDs.
  • Power modules such as diodes, rectifiers, thyristors, MOS gate drivers, power switches, power MOSFETs, IGBTs, shotkey diodes, and fast recovery diodes; transmitters; amplifiers; high-brightness LEDs.
  • Modules Sensors and the like.
  • FIG. 4 is a schematic cross-sectional view for explaining a method of manufacturing the bonded body 100.
  • the bonding copper paste 10 and the first member 3 are placed in this order on the side in which the weight of the first member 2 and the first member 2 acts.
  • the first step of preparing the laminated body 50 (FIG. 4A) and the state in which the bonding copper paste 10 receives the weight of the first member 2, or the weight of the first member 2. It also includes a second step of sintering at a predetermined temperature under a pressure of 0.01 MPa or less. As a result, the bonded body 100 is obtained (FIG. 4 (b)).
  • the direction in which the weight of the first member 2 works can also be said to be the direction in which gravity works.
  • the first step and the second step according to the present embodiment can be carried out in the same manner as the first step and the second step described above.
  • the semiconductor device 110 can be manufactured in the same manner as the manufacturing method of the bonded body 100 described above. That is, in the method of manufacturing a semiconductor device, a semiconductor element is used for at least one of a first member and a second member, and the bonding copper is placed on the side in the direction in which the weight of the first member and the first member works. Prepare a laminate in which the paste and the second member are laminated in this order, and apply the bonding copper paste in a state of receiving the weight of the first member, or the weight of the first member and 0.01 MPa or less. It is provided with a step of sintering at a predetermined temperature under the pressure of.
  • the laminate 60 is heated and the bonding copper paste 20 is sintered to obtain the bonded body 105 (FIG. 5 (b)).
  • the lead frame 15b and the semiconductor element 18 in the obtained bonded body 105 are connected by a wire 16 and sealed with a sealing resin.
  • the semiconductor device 110 is obtained by the above steps (FIG. 5 (c)).
  • the obtained semiconductor device 110 can have sufficient die shear strength and connection reliability even when bonding is performed without pressurization.
  • the semiconductor device of the present embodiment has sufficient bonding strength, and by providing a sintered body of a copper paste for bonding containing copper having a high thermal conductivity and a high melting point, it has sufficient die shear strength and connection reliability. It can be excellent in power cycle resistance as well as excellent in power cycle resistance. Further, by using the bonding copper paste of the present embodiment having excellent printability and bonding property, the above-mentioned semiconductor device can be efficiently manufactured.
  • a bonded body and a semiconductor device manufactured by using the bonding copper paste of the present embodiment has been described above, but the bonded body and the semiconductor device manufactured by using the bonding copper paste of the present embodiment are described above. It is not limited to the form.
  • the bonded body produced by using the bonding copper paste of the present embodiment may be, for example, the bonded body shown in FIGS. 6 and 8.
  • the bonded body 120 shown in FIG. 6 includes a first member 2, a second member 3, a third member 4, a fourth member 5, and a first member 2 and a second member 3.
  • such a bonded body 120 is on the side in the direction in which the weight of the third member 4 and the third member 4 acts.
  • a laminated body 70 having a third bonding copper paste 10c and a laminated portion in which the fourth member 5 is laminated in this order is prepared on the side in the direction in which the weight of the member 4 works (FIG. 7 (a)).
  • the first bonding copper paste 10a, the second bonding copper paste 10b, and the third bonding copper paste 10c are the bonding copper paste according to the present embodiment, and the first bonding copper paste.
  • the sintered body 1a is obtained by sintering 10a
  • the sintered body 1b is obtained by sintering the second bonding copper paste 10b
  • the third bonding copper paste 10c is sintered. 1c obtained a sintered body.
  • the third member 4 for example, after obtaining the bonded body 100, the third member 4, the second bonding copper paste 10b, and the second bonding body 120 are placed in the direction in which the weight of the third member 4 acts.
  • a method comprising a step of forming a laminated portion laminated in this order and sintering a second bonding copper paste 10b and a third bonding copper paste 10c in the same manner as in the method for producing the bonded body 100. You can also get it at.
  • the joined body 130 shown in FIG. 8 includes a first member 2, a second member 3, a third member 4, a fourth member 5, a fifth member 6, and a first member 2.
  • the joint portion) 1c, the sintered body (joint portion) 1d of the copper paste for joining the first member 2 and the fifth member 6, and the third member 4 and the fifth member 6 are attached to each other.
  • a sintered body (joint portion) 1e of the copper paste for joining is provided.
  • such a joint 130 is, for example, on the side in the direction in which the weight of the third member 4 and the third member 4 acts.
  • the fifth bonding copper paste 10e, the fifth member 6, the fourth bonding copper paste 10d, the first member 2, the first bonding copper paste 10a, and the second member 3 are laminated in this order.
  • a laminate 80 having the above is prepared (FIG.
  • the first bonding metal paste 10a, the third bonding copper paste 10c, and the fourth bonding body 100 are prepared in the same manner as in the manufacturing method of the bonded body 100. It can be obtained by a method including a step of sintering the bonding copper paste 10d and the fifth bonding copper paste 10e (FIG. 9 (b)).
  • the first bonding copper paste 10a, the third bonding copper paste 10c, the fourth bonding copper paste 10d, and the fifth bonding copper paste 10e are the bonding copper pastes according to the present embodiment.
  • the first bonding copper paste 10a is sintered to obtain a sintered body 1a
  • the third bonding copper paste 10c is sintered to obtain a sintered body 1c
  • the fourth bonding is performed.
  • a sintered body 1d is obtained by sintering the copper paste 10d for bonding
  • a sintered body 1e is obtained by sintering the copper paste 10e for bonding fifth.
  • the fifth member 4, the fifth member 6, and the fourth copper paste for joining are placed on the side in the direction in which the weight of the third member 4 works.
  • a laminate in which 10d, the first member 2, the first bonding copper paste 10a, and the second member 3 are laminated in this order is prepared, and the first method is similar to the method for manufacturing the bonding body 100.
  • the bonding copper paste 10a, the fourth bonding copper paste 10d, and the fifth bonding copper paste 10e are sintered, the third member 4 and the weight of the third member 4 are placed in the direction in which the weight acts.
  • a laminated portion in which the third bonding copper paste 10c and the fourth member 5 are laminated in this order is formed, and the third bonding copper paste 10c is sintered in the same manner as in the manufacturing method of the bonded body 100. It can also be obtained by a method including a step of performing.
  • the joint body 130 has a fifth bonding copper paste 10e and a fifth member on the side in the direction in which the weight of the third member 4 and the third member 4 works.
  • the bonding copper paste 10c and the fourth member 5 are laminated in this order to form a laminated portion, and the third bonding copper paste 10c and the fourth member 5 are formed in the same manner as in the manufacturing method of the bonded body 100. It can also be obtained by a method including a step of sintering the bonding copper paste 10d and the fifth bonding copper paste 10e.
  • the example of the third member 4, the fourth member 5, and the fifth member 6 is the same as the example of the second member 3.
  • the surface of the third member 4, the fourth member 5, and the fifth member 6 in contact with the sintered body of the bonding copper paste may contain metal.
  • the example of the metal that can be contained is the same as the example of the metal that can be contained in the surface where the first member and the second member are in contact with the sintered body of the copper paste for joining.
  • the first bonding copper paste 10a, the second bonding copper paste 10b, the third bonding copper paste 10c, the fourth bonding copper paste 10d, and the fifth bonding copper paste used in the above modification are used.
  • the 10e may be the same or different.
  • Example 1 CH-0200 (manufactured by Mitsui Metal Mining Co., Ltd., product name, 50% volume average particle size: 0.3 ⁇ m) 60.7 parts by mass, dihydroterpineol (manufactured by Nippon Terupen Chemical Industries, Ltd.) as a material containing sub-micro copper particles ) 8.0 parts by mass, tributyrin (boiling point: 305 ° C, manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) 3.6 parts by mass, and Fineoxocol-180T (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) 0.4
  • the parts by mass were mixed with a stirrer manufactured by Shinky Co., Ltd. (trade name: "Awatori Rentaro ARE-310", the same applies hereinafter) at 2000 rpm for 1 minute. Then, the dispersion treatment was carried out 10 times with a 3-roll mill to obtain a mixture.
  • 3L3N manufactured by Mitsui Metal Mining Co., Ltd., product name, 50% volume average particle size: 7 ⁇ m
  • a part by mass was added to the container, and the mixture was mixed with a stirrer manufactured by Shinky Co., Ltd. under the conditions of 2000 rpm and 1 minute.
  • the dispersion treatment was carried out 5 times with a 3-roll mill to obtain a copper paste for bonding.
  • Example 2 Example 2 and reference example 1
  • the solvent amount of the paste in Example 1 was reduced to adjust the metal particle concentration to 89% by mass.
  • Reference Example 1 a copper paste for bonding was prepared in the same manner as in Example 1 except that the composition of the copper paste for bonding was changed to the composition shown in Table 1 (the unit of the numerical value is parts by mass).
  • viscosity The viscosity of the copper paste for bonding conforms to the viscosity measurement method of solder paste (JIS Z 3284-1: 2014) standardized by JIS, and the viscometer TV-33 (manufactured by Toki Sangyo Co., Ltd., product name). Using an SPP rotor as a measuring tool, the measurement was performed under the conditions of a rotation speed of 2.5 rpm and a measurement time of 144 seconds.
  • Printing was performed on a copper plate by a screen printing machine under the following conditions, and the printability was evaluated.
  • the opening sizes were 3 mm ⁇ , 5 mm ⁇ , 7 mm ⁇ , and 10 mm ⁇ .
  • a stainless steel metal mask (thickness: 200 ⁇ m) with openings for each print shape (3 mm ⁇ , 5 mm ⁇ , 7 mm ⁇ , and 10 mm ⁇ ) is placed on a copper plate, and stencil printing with a metal squeegee is used to print the outbound route: speed.
  • the bonding copper paste was printed under the conditions of 150 mm / s, printing pressure 0.2 MPa, return path: 100 mm / s, printing pressure 0.1 MPa.
  • a stainless steel metal mask (thickness: 200 ⁇ m) having openings of each print shape (3 mm ⁇ , 5 mm ⁇ , 7 mm ⁇ , and 10 mm ⁇ ) is placed on a copper plate, and stencil printing using a metal squeegee is performed.
  • the bonding copper paste was printed under the conditions of a speed of 150 mm / s, a printing pressure of 0.2 MPa, a return path: 100 mm / s, and a printing pressure of 0.1 MPa.
  • the Si chip on which the Ni layer was formed was placed on the printed copper paste, and dried at 60 ° C.
  • the sample on which the chip was placed was set in a tube furnace (manufactured by Earl Deck Co., Ltd.), and argon gas was flowed at 3 L / min for 5 minutes to replace the sample.
  • hydrogen gas was flowed at 500 mL / min, and the temperature was raised to the junction temperature in 30 minutes.
  • the temperature was maintained at 225 ° C. for 60 minutes while flowing hydrogen gas, and then cooled to 200 ° C. for 15 minutes.
  • the sample was forcibly cooled from the outside of the tube furnace by an air blow to bring the sample temperature to 60 ° C. or lower, and then the sample was taken out into the air.
  • ⁇ Joined area ratio> The sample of the joint was analyzed by an ultrasonic flaw detector (Insight-300, manufactured by Insight Co., Ltd.) to obtain an ultrasonic flaw detector image (SAT image) of the joint.
  • SAT image ultrasonic flaw detector image
  • the obtained SAT image was binarized, and the joint area ratio (area%) with respect to the chip area was calculated.
  • the joint area ratio was 99% or more for all opening sizes.
  • the copper pastes for bonding in Examples 1 and 2 can be printed well with an opening size of 3 to 10 mm ⁇ under printing conditions assuming automatic printing, and achieve sufficient bondability. It was confirmed that it could be done.
  • Dihydroterpineol is a single bond obtained by hydrogenating the double bond contained in the molecular structure of tarpineol.
  • the molecular structure and properties are considered to be very similar to those of tarpineol, but the viscosity of the copper paste is increased. It can be said that it is an unexpected effect that it can be reduced and sufficient bondability can be obtained.

Abstract

接合用銅ペーストは、金属粒子と分散媒とを含有し、金属粒子として、銅粒子を含み、分散媒として、ジヒドロターピネオールを含む。接合体の製造方法は、第１の部材と、第２の部材と、第１の部材及び第２の部材を接合する接合部とを備える接合体の製造方法であって、第１の部材及び第２の部材の少なくとも一方の接合面に上記接合用銅ペーストを印刷し、第１の部材、接合用銅ペースト、第２の部材がこの順に積層されている積層構造を有する積層体を用意する第１の工程と、積層体の接合用銅ペーストを焼結する第２の工程とを備える。

Description

接合用銅ペースト、接合体の製造方法及び接合体
　本発明は、接合用銅ペースト、接合体の製造方法及び接合体に関する。
　半導体装置を製造する際、半導体素子とリードフレーム等（支持部材）とを接合させるため、さまざまな接合材が用いられている。半導体装置の中でも、１５０℃以上の高温で動作させるパワー半導体、ＬＳＩ等の接合には、接合材として高融点鉛はんだが用いられてきた。近年、半導体素子の高容量化及び省スペース化により動作温度が高融点鉛はんだの融点近くまで上昇しており、接続信頼性を確保することが難しくなってきている。一方で、ＲｏＨＳ規制強化に伴い、鉛を含有しない接合材が求められている。
　これまでにも、鉛はんだ以外の材料を用いた半導体素子の接合が検討されている。例えば、下記特許文献１には、半導体素子と電極とを接合するための接合材として、平均粒径が１ｎｍ～５０μｍの酸化第２銅粒子及び還元剤を含む接合材が開示されている。また、下記特許文献２には、銅ナノ粒子と、銅マイクロ粒子もしくは銅サブマイクロ粒子、あるいはそれら両方を含む接合材が開示されている。
特許第５００６０８１号 特開２０１４－１６７１４５号公報
　ところで、半導体装置の製造における量産プロセスを考慮すると、接合材には、スクリーン印刷機等の自動印刷機による印刷プロセスに適した印刷性を有していることが求められる。一般に、分散媒に金属粒子を分散させたペーストは、有機溶媒等の分散媒を配合して低粘度化することによって印刷性を向上させることができる。しかし、銅粒子を含むペーストの場合、粒子濃度が低すぎると充分な接合強度が得られにくくなるなど接合性に影響が出ることがあり、自動印刷における印刷条件でカスレや欠けが無く印刷できる印刷性と、接合性とを両立させることは必ずしも容易ではない。
　本発明は、上記事情に鑑みてなされたものであり、充分な接合性を維持しつつ印刷性の向上を可能とする接合用銅ペースト、並びに、それを用いる接合体の製造方法及び接合体を提供することを目的とする。
　本発明の一側面は、金属粒子と分散媒とを含有し、金属粒子として銅粒子を含み、分散媒としてジヒドロターピネオールを含む接合用銅ペーストに関する。
　上記接合用銅ペーストは、上記構成を有することにより、充分な接合性を維持しつつ印刷性を向上させることができる。上記接合用銅ペーストによれば、スクリーン印刷機等の自動印刷機を用いる量産プロセスによって接合体を効率よく製造することができる。
　このような効果が得られる理由は明らかではないが、ジヒドロターピネオールが銅粒子との親和性に優れていることで銅粒子の分散性が向上し、充分な銅粒子濃度において低粘度化が可能となり、印刷性と接合性との両立が可能になったものと考えられる。また、ジヒドロターピネオールがペーストのチクソ性を高めることができることで、印刷時の流動性と、印刷後のペーストの形状保持力とが高水準で両立されることも上記効果が得られる要因の一つであると本発明者らは推察する。
　上記接合用銅ペーストは、金属粒子の含有量が、接合用銅ペースト全量を基準として、８５～９８質量％であってもよい。この場合、接合強度を確保しやすくなり、接合する部材の大きさ（例えば、半導体素子のサイズ）が拡大することへの対応が容易となる。
　上記接合用銅ペーストは、分散媒として、沸点が３００℃以上である化合物を更に含むことができる。この場合、焼結開始直前まで接合用銅ペーストに可塑性と密着性が付与され、無加圧での接合が容易になる。
　上記接合用銅ペーストは、２５℃における粘度が１００～２００Ｐａ・ｓであってもよい。この場合、自動印刷機への適合性が更に向上する。
　銅粒子の含有量は、金属粒子の全質量を基準として、８０～１００質量％であってもよい。
　上記接合用銅ペーストは、スクリーン印刷用であってもよい。
　なお、本明細書においてスクリーン印刷とは、ステンシル印刷とも称し、孔（開口）を有する版にペーストを擦りつける印刷方式を意味する。スキージ及びスクレーパー等については特に限定されず、公知のものを適宜適用することができる。
　接合用銅ペーストは、銅粒子として、体積平均粒径が０．１２～０．８μｍであるサブマイクロ銅粒子と、最大径が２～５０μｍであり、アスペクト比が３．０以上であるフレーク状のマイクロ銅粒子とを含んでいてもよい。この場合、無加圧での接合に好適である。
　なお、本明細書において無加圧とは、接合用銅ペーストが、接合する部材の重さのみ（すなわち、部材の重さ以外の圧力を受けていない）、又はその重さに加え、０．０１ＭＰａ以下の微圧力を受けている状態を意味する。
　接合用銅ペーストにおける上記サブマイクロ銅粒子の含有量は、銅粒子の全質量を基準として、３０～９０質量％であり、上記マイクロ銅粒子の含有量は、銅粒子の全質量を基準として、１０～７０質量％であってもよい。
　接合用銅ペーストは、無加圧接合用であってよい。
　本発明の他の側面は、第１の部材と、第２の部材と、第１の部材及び第２の部材を接合する接合部と、を備える接合体の製造方法であって、第１の部材及び第２の部材の少なくとも一方の接合面に上記接合用銅ペーストを印刷し、第１の部材、接合用銅ペースト、及び第２の部材がこの順に積層されている積層構造を有する積層体を用意する第１の工程と、積層体の接合用銅ペーストを焼結する第２の工程と、を備える接合体の製造方法に関する。この製造方法によれば、上記接合用銅ペーストを用いることにより、印刷性と接合性との両立が可能となり、接合体を効率よく製造することができる。
　上記印刷はスクリーン印刷であってもよい。
　上記第２の工程において、接合用銅ペーストを無加圧で加熱して焼結してもよい。この場合、無加圧接合によって接合される部材へのダメージを低減できる。
　上記の第１の部材及び第２の部材の少なくとも一方は半導体素子であってよい。この場合、接合体として半導体装置を得ることができる。
　本発明の他の側面は、第１の部材、第２の部材、及び、第１の部材と第２の部材とを接合する接合部を備え、接合部が、上記接合用銅ペーストの焼結体からなる接合体に関する。
　上記の第１の部材及び第２の部材の少なくとも一方は半導体素子であってよい。すなわち、接合体は半導体装置であってよい。
　本発明によれば、充分な接合性を維持しつつ印刷性の向上を可能とする接合用銅ペースト、並びに、それを用いる接合体の製造方法及び接合体を提供することができる。
スクリーン印刷について説明するための模式図である。 本実施形態の接合用銅ペーストを用いて製造される接合体の一例を示す模式断面図である。 本実施形態の接合用銅ペーストを用いて製造される半導体装置の一例を示す模式断面図である。 図２に示す接合体の製造方法を説明するための模式断面図である。 図３に示す半導体装置の製造方法を説明するための模式断面図である。 本実施形態の接合用銅ペーストを用いて製造される接合体の一例を示す模式断面図である。 図６に示す接合体の製造方法を説明するための模式断面図である。 本実施形態の接合用銅ペーストを用いて製造される接合体の一例を示す模式断面図である。 図８に示す接合体の製造方法を説明するための模式断面図である。
　まず、本実施形態の接合用銅ペーストの詳細について説明する。
＜接合用銅ペースト＞
　本実施形態の接合用銅ペーストは、金属粒子と、分散媒とを含有し、金属粒子として銅粒子を含み、分散媒としてジヒドロターピネオールを含む。なお、本明細書では、便宜上、複数の銅粒子の集合も「銅粒子」と称する。銅粒子以外の金属粒子についても同様である。
（銅粒子）
　銅粒子としては、サブマイクロ銅粒子、マイクロ銅粒子、及びこれら以外の銅粒子が挙げられる。
［サブマイクロ銅粒子］
　サブマイクロ銅粒子は、０．０１μｍ以上１．００μｍ未満の粒径を有する銅粒子である。サブマイクロ銅粒子は、好ましくは、１５０℃以上３００℃以下の温度範囲で焼結性を有する。サブマイクロ銅粒子は、粒径が０．０１～０．８０μｍの銅粒子を含むことが好ましい。サブマイクロ銅粒子は、粒径が０．０１～０．８０μｍの銅粒子を１０質量％以上含んでいてよく、２０質量％以上含んでいてもよく、３０質量％以上含んでいてもよく、１００質量％含んでいてもよい。銅粒子の粒径は、例えば、ＳＥＭ像から算出することができる。銅粒子の粉末を、ＳＥＭ用のカーボンテープ上にスパチュラで載せ、ＳＥＭ用サンプルとする。このＳＥＭ用サンプルをＳＥＭ装置により５０００倍で観察する。このＳＥＭ像の銅粒子に外接する四角形を画像処理ソフトにより作図し、その一辺をその粒子の粒径とする。
　サブマイクロ銅粒子の体積平均粒径は、好ましくは０．０１～０．８０μｍである。サブマイクロ銅粒子の体積平均粒径が０．０１μｍ以上であれば、サブマイクロ銅粒子の合成コストの抑制、良好な分散性、表面処理剤の使用量の抑制といった効果が得られやすくなる。サブマイクロ銅粒子の体積平均粒径が０．８０μｍ以下であれば、サブマイクロ銅粒子の焼結性が優れるという効果が得られやすくなる。上記効果がより一層奏される観点から、サブマイクロ銅粒子の体積平均粒径は、０．０２μｍ以上、０．０５μｍ以上、０．１０μｍ以上、０．１１μｍ以上、０．１２μｍ以上、０．１５μｍ以上、０．２μｍ以上又は０．３μｍ以上であってもよい。また、上記効果がより一層奏される観点から、サブマイクロ銅粒子の体積平均粒径は、０．６０μｍ以下、０．５０μｍ以下、０．４５μｍ以下又は０．４０μｍ以下であってもよい。サブマイクロ銅粒子の体積平均粒径は、例えば、０．０１～０．６０μｍ、０．０１～０．５０μｍ、０．０２～０．８０μｍ、０．０５～０．８０μｍ、０．１０～０．８０μｍ、０．１１～０．８０μｍ、０．１２～０．８０μｍ、０．１５～０．８０μｍ、０．１５～０．６０μｍ、０．２０～０．５０μｍ、０．３０～０．４５μｍ、又は、０．３０～０．４０μｍであってよい。
　本明細書において体積平均粒径とは、５０％体積平均粒径を意味する。金属粒子（例えば銅粒子）の体積平均粒径は、例えば、以下の方法で測定することができる。まず、原料となる金属粒子、又は、金属ペーストから揮発成分を除去して得られる乾燥金属粒子を、分散剤を用いて分散媒に分散させる。次いで、得られた分散体の体積平均粒径を光散乱法粒度分布測定装置（例えば、島津ナノ粒子径分布測定装置（ＳＡＬＤ－７５００ｎａｎｏ、株式会社島津製作所製））で測定する。光散乱法粒度分布測定装置を用いる場合、分散媒としては、ヘキサン、トルエン、α－テルピネオール、４－メチル－１，３－ジオキソラン－２－オン等を用いることができる。
　サブマイクロ銅粒子の形状は、特に限定されるものではない。サブマイクロ銅粒子の形状としては、例えば、球状、塊状、針状、柱状、フレーク状、略球状及びこれらの凝集体が挙げられる。分散性及び充填性の観点から、サブマイクロ銅粒子の形状は、球状、略球状又はフレーク状であってよく、燃焼性、分散性、フレーク状のマイクロ粒子（例えば、フレーク状のマイクロ銅粒子）との混合性等の観点から、球状又は略球状であってもよい。本明細書において、「フレーク状」とは、板状、鱗片状等の平板状の形状を包含する。
　サブマイクロ銅粒子のアスペクト比は、分散性、充填性、及びフレーク状のマイクロ粒子（例えば、フレーク状のマイクロ銅粒子）との混合性の観点から、５．０以下であってよく、３．０以下であってもよく、２．５以下であってもよく、２．０以下であってもよい。本明細書において、「アスペクト比」とは、「粒子の長辺／粒子の厚さ」を示す。粒子の長辺及び粒子の厚さは、例えば、粒子のＳＥＭ像から求めることができる。
　サブマイクロ銅粒子は、サブマイクロ銅粒子の分散性の観点から、表面処理剤で処理されていてもよい。表面処理剤は、例えば、サブマイクロ銅粒子の表面に水素結合等によって吸着していてよく、サブマイクロ銅粒子と反応してサブマイクロ銅粒子の表面に結合していてもよい。すなわち、サブマイクロ銅粒子が特定の表面処理剤由来の化合物を有していてもよい。表面処理剤は、接合用銅ペーストに含まれる有機化合物に包含される。
　表面処理剤としては、例えば、炭素数２～１８の有機酸が挙げられる。炭素数２～１８の有機酸としては、例えば、酢酸、プロパン酸、ブタン酸、ペンタン酸、ヘキサン酸、ヘプタン酸、カプリル酸、メチルヘプタン酸、エチルヘキサン酸、プロピルペンタン酸、ペラルゴン酸、メチルオクタン酸、エチルヘプタン酸、プロピルヘキサン酸、カプリン酸、メチルノナン酸、エチルオクタン酸、プロピルヘプタン酸、ブチルヘキサン酸、ウンデカン酸、メチルデカン酸、エチルノナン酸、プロピルオクタン酸、ブチルヘプタン酸、ラウリン酸、メチルウンデカン酸、エチルデカン酸、プロピルノナン酸、ブチルオクタン酸、ペンチルヘプタン酸、トリデカン酸、メチルドデカン酸、エチルウンデカン酸、プロピルデカン酸、ブチルノナン酸、ペンチルオクタン酸、ミリスチン酸、メチルトリデカン酸、エチルドデカン酸、プロピルウンデカン酸、ブチルデカン酸、ペンチルノナン酸、ヘキシルオクタン酸、ペンタデカン酸、メチルテトラデカン酸、エチルトリデカン酸、プロピルドデカン酸、ブチルウンデカン酸、ペンチルデカン酸、ヘキシルノナン酸、パルミチン酸、メチルペンタデカン酸、エチルテトラデカン酸、プロピルトリデカン酸、ブチルドデカン酸、ペンチルウンデカン酸、ヘキシルデカン酸、ヘプチルノナン酸、ヘプタデカン酸、オクタデカン酸、メチルシクロヘキサンカルボン酸、エチルシクロヘキサンカルボン酸、プロピルシクロヘキサンカルボン酸、ブチルシクロヘキサンカルボン酸、ペンチルシクロヘキサンカルボン酸、ヘキシルシクロヘキサンカルボン酸、ヘプチルシクロヘキサンカルボン酸、オクチルシクロヘキサンカルボン酸、ノニルシクロヘキサンカルボン酸等の飽和脂肪酸；オクテン酸、ノネン酸、メチルノネン酸、デセン酸、ウンデセン酸、ドデセン酸、トリデセン酸、テトラデセン酸、ミリストレイン酸、ペンタデセン酸、ヘキサデセン酸、パルミトレイン酸、サビエン酸、オレイン酸、バクセン酸、リノール酸、リノレイン酸、リノレン酸等の不飽和脂肪酸；テレフタル酸、ピロメリット酸、ｏ－フェノキシ安息香酸、メチル安息香酸、エチル安息香酸、プロピル安息香酸、ブチル安息香酸、ペンチル安息香酸、ヘキシル安息香酸、ヘプチル安息香酸、オクチル安息香酸、ノニル安息香酸等の芳香族カルボン酸が挙げられる。有機酸は、一種を単独で使用してもよく、二種以上を組み合わせて使用してもよい。このような有機酸と上記サブマイクロ銅粒子とを組み合わせることで、サブマイクロ銅粒子の分散性と焼結時における有機酸の脱離性を両立できる傾向にある。
　表面処理剤の処理量は、サブマイクロ銅粒子の分散性の観点から、表面処理後のサブマイクロ銅粒子の全質量を基準として、０．０７～２．１０質量％、０．１０～１．６０質量％又は０．２０～１．１０質量％であってよい。表面処理剤の処理量は、表面処理後のサブマイクロ銅粒子の全質量を基準として、０．０７質量％以上、０．１０質量％以上又は０．２０質量％以上であってよい。表面処理剤の処理量は、表面処理後のサブマイクロ銅粒子の全質量を基準として、２．１０質量％以下、１．６０質量％以下又は１．１０質量％以下であってよい。
　表面処理剤の処理量は、サブマイクロ銅粒子の表面に一分子層～三分子層付着する量であってもよい。この処理量は、以下の方法により測定される。大気中、７００℃で２時間処理したアルミナ製るつぼ（例えば、アズワン製、型番：１－７７４５－０７）に、表面処理されたサブマイクロ銅粒子をＷ１（ｇ）量り取り、大気中７００℃で１時間焼成する。その後、水素中、３００℃で１時間処理し、るつぼ内の銅粒子の質量Ｗ２（ｇ）を計測する。次いで、下記式に基づき、表面処理剤の処理量を算出する。
　表面処理剤の処理量（質量％）＝（Ｗ１－Ｗ２）／Ｗ１×１００
　サブマイクロ銅粒子としては、市販されているものを用いることができる。市販されているサブマイクロ銅粒子を含む材料としては、例えば、ＣＨ－０２００（三井金属鉱業株式会社製、体積平均粒径０．３６μｍ）、ＨＴ－１４（三井金属鉱業株式会社製、体積平均粒径０．４１μｍ）、ＣＴ－５００（三井金属鉱業株式会社製、体積平均粒径０．７２μｍ）、Ｔｎ－Ｃｕ１００（太陽日産株式会社製、体積平均粒径０．１２μｍ）及びＣｕ－Ｃ－４０（福田金属箔粉工業株式会社製、体積平均粒径０．２μｍ）が挙げられる。
　サブマイクロ銅粒子の含有量は、接合用銅ペーストに含まれる銅粒子の全質量を基準として、３０質量％以上、３５質量％以上、４０質量％以上又は５０質量％以上であってよく、９０質量％以下又は８５質量％以下であってよい。また、サブマイクロ銅粒子の含有量は、接合用銅ペーストに含まれる銅粒子の全質量を基準として、３０～９０質量％、３５～９０質量％、４０～８５質量％又は５０～８５質量％であってよい。サブマイクロ銅粒子の含有量が上記範囲内であれば、接合用銅ペーストを焼結させて製造される接合体の接合強度を確保することが容易となる。接合用銅ペーストをマイクロデバイスの接合に用いる場合は、マイクロデバイスが良好なダイシェア強度及び接続信頼性を示す傾向にある。
［マイクロ銅粒子］
　マイクロ銅粒子は、１μｍ以上５０μｍ未満の粒径を有する銅粒子である。マイクロ銅粒子は、粒径が２．０～５０μｍの銅粒子を含むことが好ましい。マイクロ銅粒子は、粒径が２．０～５０μｍの銅粒子を５０質量％以上含んでいてよく、７０質量％以上含んでいてもよく、８０質量％以上含んでいてもよく、１００質量％含んでいてもよい。
　マイクロ銅粒子の体積平均粒径は、好ましくは２．０～５０μｍである。マイクロ銅粒子の体積平均粒径が上記範囲内であれば、接合用銅ペーストを焼結した際の体積収縮、ボイドの発生等を低減でき、接合用銅ペーストを焼結させて製造される接合体の接合強度を確保することが容易となる。接合用銅ペーストをマイクロデバイスの接合に用いる場合は、マイクロデバイスが良好なダイシェア強度及び接続信頼性を示す傾向にある。上記効果がより一層奏される観点から、マイクロ銅粒子の体積平均粒径は、２．０～２０μｍ、２．０～１０μｍ、３．０～２０μｍ又は３．０～１０μｍであってもよい。マイクロ銅粒子の体積平均粒径は、２．０μｍ以上又は３．０μｍ以上であってよい。マイクロ銅粒子の体積平均粒径は、５０μｍ以下、２０μｍ以下又は１０μｍ以下であってよい。
　マイクロ銅粒子の形状は、特に限定されるものではない。マイクロ銅粒子の形状としては、例えば、球状、塊状、針状、フレーク状、略球状、及びこれらの凝集体が挙げられる。これらの中でも、好ましいマイクロ銅粒子の形状はフレーク状である。マイクロ銅粒子は、フレーク状のマイクロ銅粒子を５０質量％以上含んでいてよく、７０質量％以上含んでいてもよく、８０質量％以上含んでいてもよく、１００質量％含んでいてもよい。
　フレーク状のマイクロ銅粒子を用いることで、接合用銅ペースト内のマイクロ銅粒子が、接合面に対して略平行に配向することとなり、接合用銅ペーストを焼結させたときの接合面方向の体積収縮を抑制でき、接合用銅ペーストを焼結させて製造される接合体の接合強度を確保することが容易となる。接合用銅ペーストをマイクロデバイスの接合に用いる場合は、マイクロデバイスが良好なダイシェア強度及び接続信頼性を示す傾向にある。上記効果がより一層奏される観点から、フレーク状のマイクロ銅粒子のアスペクト比は、好ましくは３．０以上であり、より好ましくは４．０以上であり、更に好ましくは６．０以上である。
　フレーク状のマイクロ銅粒子の最大径及び平均最大径は、２．０～５０μｍ、３．０～５０μｍ又は３．０～２０μｍであってよい。フレーク状のマイクロ銅粒子の最大径及び平均最大径は、例えば、粒子のＳＥＭ像から求めることができる。フレーク状のマイクロ銅粒子の最大径及び平均最大径は、例えば、フレーク状のマイクロ銅粒子の長径Ｘ及び長径の平均値Ｘａｖとして求められる。長径Ｘは、フレーク状のマイクロ銅粒子の三次元形状において、フレーク状のマイクロ銅粒子に外接する平行二平面のうち、この平行二平面間の距離が最大となるように選ばれる平行二平面の距離である。
　マイクロ銅粒子において、表面処理剤の処理の有無は特に限定されるものではない。分散安定性及び耐酸化性の観点から、マイクロ銅粒子は表面処理剤で処理されていてもよい。すなわち、マイクロ銅粒子が表面処理剤由来の化合物を有していてもよい。表面処理剤は、マイクロ銅粒子の表面に水素結合等によって吸着していてよく、マイクロ銅粒子と反応してマイクロ銅粒子の表面に結合していてもよい。
　表面処理剤は、接合時の加熱により除去されるものであってもよい。このような表面処理剤としては、例えば、ドデカン酸、パルミチン酸、ヘプタデカン酸、ステアリン酸、アラキジン酸、リノール酸、リノレイン酸、オレイン酸等の脂肪族カルボン酸；テレフタル酸、ピロメリット酸、ｏ－フェノキシ安息香酸等の芳香族カルボン酸；セチルアルコール、ステアリルアルコール、イソボルニルシクロヘキサノール、テトラエチレングリコール等の脂肪族アルコール；ｐ－フェニルフェノール等の芳香族アルコール；オクチルアミン、ドデシルアミン、ステアリルアミン等のアルキルアミン；ステアロニトリル、デカンニトリル等の脂肪族ニトリル；アルキルアルコキシシラン等のシランカップリング剤；ポリエチレングリコール、ポリビニルアルコール、ポリビニルピロリドン、シリコーンオリゴマー等の高分子処理材などが挙げられる。表面処理剤は、一種を単独で使用してもよく、二種以上を組み合わせて使用してもよい。
　マイクロ銅粒子としては、市販されているものを用いることができる。市販されているマイクロ銅粒子を含む材料としては、例えば、１０５０ＹＦ（三井金属鉱業株式会社製、体積平均粒径１．７μｍ）、ＭＡ－Ｃ０２５ＫＦＤ（三井金属鉱業株式会社製、体積平均粒径７．５μｍ）、３Ｌ３（福田金属箔粉工業株式会社製、体積平均粒径８．０μｍ）、２Ｌ３Ｎ（福田金属箔粉工業株式会社製、体積平均粒径９．９μｍ）、３Ｌ３Ｎ（福田金属箔粉工業株式会社製、体積平均粒径７μｍ）及び１１１０Ｆ（三井金属鉱業株式会社製、体積平均粒径３．８μｍ）が挙げられる。
　マイクロ銅粒子の含有量は、接合用銅ペーストに含まれる銅粒子の全質量を基準として、１０質量％以上、１５質量％以上又は２０質量％以上であってよく、７０質量％以下、５０質量％以下、４５質量％以下又は４０質量％以下であってよい。また、マイクロ銅粒子の含有量は、接合用銅ペーストに含まれる銅粒子の全質量を基準として、１０～７０質量％、１０～６５質量％、１０～５０質量％、１５～６０質量％、１５～５０質量％、又は１５～４５質量％であってよい。マイクロ銅粒子の含有量が、上記範囲内であれば、接合部（例えば焼結体）の剥離、ボイド及びクラックの発生を抑制して接合強度を確保することができる。接合用銅ペーストをマイクロデバイスの接合に用いる場合は、マイクロデバイスが良好なダイシェア強度及び接続信頼性を示す傾向にある。フレーク状のマイクロ銅粒子の含有量は、上記のマイクロ銅粒子の含有量の範囲と同じであってよい。フレーク状のマイクロ銅粒子の含有量がこのような範囲にある場合、上記効果がより一層奏される傾向がある。
［その他の銅粒子］
　サブマイクロ銅粒子及びマイクロ銅粒子以外の銅粒子としては、銅ナノ粒子が挙げられる。銅ナノ粒子とは、０．０１μｍ未満の粒径を有する銅粒子を指す。銅ナノ粒子は一般的に表面にカルボン酸やアミンで被覆（表面被覆材という）されている。銅ナノ粒子は銅マイクロ粒子に比べて比表面積が大きく、単位質量当たりに占める表面被覆材の割合が増加する傾向にある。そのため焼結時（加熱時）に脱離する表面被覆材が多くなるため、銅マイクロ粒子に比べて焼結時の体積収縮が増える傾向ある。体積収縮を少なくする観点から、銅ナノ粒子の含有量は、銅粒子の全質量を基準として、１０質量％以下が好ましく、５質量％以下がより好ましく、含まないことがさらに好ましい。
　本実施形態の接合用銅ペーストにおける銅粒子の含有量は、接合用銅ペーストに含まれる金属粒子の全質量を基準として、８０～１００質量％であってもよく、９０～１００質量％であってもよく、９５～１００質量％であってもよい。
　本実施形態の接合用銅ペーストは、サブマイクロ銅粒子及びマイクロ銅粒子を含むことがより好ましい。サブマイクロ銅粒子とマイクロ銅粒子とを併用する場合、乾燥に伴う体積収縮及び焼結収縮が抑制されやすく、焼結時に接合用銅ペーストが接合面から剥離しにくくなる。すなわち、サブマイクロ銅粒子とマイクロ銅粒子とを併用することで、接合用銅ペーストを焼結させたときの体積収縮が抑制され、接合体はより充分な接合強度を有することができる。サブマイクロ銅粒子とマイクロ銅粒子とを併用した接合用銅ペーストをマイクロデバイスの接合に用いる場合は、マイクロデバイスがより良好なダイシェア強度及び接続信頼性を示す傾向がある。
　サブマイクロ銅粒子の含有量及びマイクロ銅粒子の含有量の合計は、接合用銅ペーストに含まれる金属粒子の全質量を基準として、８０～１００質量％であってよい。サブマイクロ銅粒子の含有量及びマイクロ銅粒子の含有量の合計が上記範囲内であれば、接合用銅ペーストを焼結した際の体積収縮を充分に低減でき、接合用銅ペーストを焼結させて製造される接合体の接合強度を確保することが容易となる。接合用銅ペーストをマイクロデバイスの接合に用いる場合は、マイクロデバイスが良好なダイシェア強度及び接続信頼性を示す傾向にある。上記効果が一層奏される観点から、サブマイクロ銅粒子の含有量及びマイクロ銅粒子の含有量の合計は、金属粒子の全質量を基準として、９０質量％以上であってもよく、９５質量％以上であってもよく、１００質量％であってもよい。
　本実施形態の接合用銅ペーストは、体積平均粒径が０．１２～０．８μｍであるサブマイクロ銅粒子と、最大径が２～５０μｍであり、アスペクト比が３．０以上であるフレーク状のマイクロ銅粒子とを含んでいてもよい。この場合、無加圧での接合に好適である。この場合の接合用銅ペーストにおける上記サブマイクロ銅粒子の含有量は、銅粒子の全質量を基準として、３０～９０質量％であり、上記マイクロ銅粒子の含有量は、銅粒子の全質量を基準として、１０～７０質量％であってもよい。
［その他の金属粒子］
　本実施形態の接合用銅ペーストは、銅粒子以外の金属粒子（「その他の金属粒子」ともいう。）を含むことができる。
　その他の金属粒子としては、例えば、亜鉛、ニッケル、銀、金、パラジウム、白金等の粒子が挙げられる。その他の金属粒子の体積平均粒径は、０．０１～１０μｍ、０．０１～５μｍ又は０．０５～３μｍであってよい。その他の金属粒子の形状は、特に限定されるものではない。その他の金属粒子の含有量は、充分な接合性を得る観点から、接合用銅ペーストに含まれる金属粒子の全質量を基準として、２０質量％未満であってよく、１０質量％以下であってもよく、５質量％以下であってもよく、１質量％以下であってもよく、０質量％であってもよい。
　本実施形態の接合用銅ペーストにおける金属粒子の含有量は、接合用銅ペースト全量を基準として、８５～９８質量％であってもよく、８５～９５質量％であってもよく、８５～９０質量％であってもよく、８７～８９質量％であってもよい。
（分散媒）
　分散媒は、金属粒子を分散する機能を有するものであれば特に限定されるものではなく、揮発性のものであってもよい。揮発性の分散媒としては、例えば、１価アルコール、多価アルコール等のアルコール類、エーテル類、エステル類、酸アミド、脂肪族炭化水素、芳香族炭化水素等が挙げられる。具体的には、シクロヘキサノール、エチレングリコール、ジエチレングリコール、プロピレングリコール、ブチレングリコール、α－ターピネオール（α－テルピネオール）、ジヒドロターピネオール（ジヒドロテルピネーオール）等のアルコール類；ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、ジエチレングリコールジブチルエーテル、ジエチレングリコールブチルメチルエーテル、ジエチレングリコールイソプロピルメチルエーテル、トリエチレングリコールジメチルエーテル、トリエチレングリコールブチルメチルエーテル、プロピレングリコールジメチルエーテル、プロピレングリコールジエチルエーテル、プロピレングリコールジブチルエーテル、プロピレングリコールジプロピルエーテル、トリプロピレングリコールジメチルエーテル等のエーテル類；エチレングリコールエチルエーテルアセテート、エチレングリコールブチルエーテルアセテート、ジエチレングリコールエチルエーテルアセテート、ジエチレングリコールブチルエーテルアセテート、ジプロピレングリコールメチルエーテルアセテート（ＤＰＭＡ）、乳酸エチル、乳酸ブチル、γ－ブチロラクトン、炭酸プロピレン等のエステル類；Ｎ－メチル－２－ピロリドン、Ｎ，Ｎ－ジメチルアセトアミド、Ｎ，Ｎ－ジメチルホルムアミド等の酸アミド；シクロヘキサン、オクタン、ノナン、デカン、ウンデカン等の脂肪族炭化水素；ベンゼン、トルエン、キシレン等の芳香族炭化水素などが挙げられる。
　本実施形態の接合用銅ペーストは、印刷性と接合性とを両立させる観点から、分散媒として、ジヒドロターピネオールを含む。
　分散媒の含有量は、接合用銅ペーストの全質量を基準として、２質量％以上、５質量％以上又は１０質量％以上であってよく、５０質量％以下、３０質量％以下、２０質量％以下又は１５質量％以下であってもよい。例えば、分散媒の含有量は、接合用銅ペーストの全質量を基準として、２～５０質量％であってよく、５～３０質量％であってもよく、５～２０質量％であってもよい。また、分散媒の含有量は、接合用銅ペーストに含まれる金属粒子の全質量を１００質量部として、２～５０質量部であってよく、５～５０質量部であってよく、２～１５質量部であってよく、５～１５質量部であってよく、１０～１５質量部であってよく、１１～１３質量部であってよい。分散媒の含有量が上記範囲内であれば、接合用銅ペーストをより適切な粘度に調整でき、また、銅粒子の焼結を阻害しにくい。
　本実施形態の接合用銅ペーストにおけるジヒドロターピネオールの含有量は、分散媒の全質量を基準として、５０～１００質量％であってもよく、５０～９０質量％であってもよく、６０～８０質量％であってもよく、１００質量％であってもよい。
　接合用銅ペーストは、分散媒として、３００℃以上の沸点を有する化合物（以下、高沸点分散媒という場合もある）を含むことが好ましい。高沸点分散媒を含むことで、焼結開始直前まで接合用銅ペーストに可塑性と密着性が付与され、無加圧での接合が容易になる。高沸点分散媒の沸点は、接合用銅ペーストの焼結時において、焼結及び緻密化を妨げず、接合温度に達した際に速やかに蒸発し除去される観点から、３００～４５０℃であってもよく、３０５～４００℃であってもよく、３１０～３８０℃であってもよい。なお、沸点は、大気圧下（１気圧）における温度を指す。。また、本明細書において、３００℃未満の沸点を有する分散媒を低沸点分散媒という場合もある。
　高沸点分散媒としては、イソボルニルシクロヘキサノール（ＭＴＰＨ、日本テルペン化学株式会社製）、ステアリン酸ブチル、エキセパールＢＳ（花王株式会社製）、ステアリン酸ステアリル、エキセパールＳＳ（花王株式会社製）、ステアリン酸２－エチルヘキシル、エキセパールＥＨ－Ｓ（花王株式会社製）、ステアリン酸イソトリデシル、エキセパールＴＤ－Ｓ（花王株式会社製）、ヘプタデカン、オクタデカン、ノナデカン、エイコサン、ヘネイコサン、ドコサン、メチルヘプタデカン、トリデシルシクロヘキサン、テトラデシルシクロヘキサン、ペンタデシルシクロヘキサン、ヘキサデシルシクロヘキサン、ウンデシルベンゼン、ドデシルベンゼン、テトラデシルベンゼン、トリデシルベンゼン、ペンタデシルベンゼン、ヘキサデシルベンゼン、ヘプタデシルベンゼン、ノニルナフタレン、ジフェニルプロパン、オクタン酸オクチル、ミリスチン酸メチル、ミリスチン酸エチル、リノール酸メチル、ステアリン酸メチル、トリエチレングリコールビス（２－エチルヘキサン酸）、クエン酸トリブチル、セバシン酸ジブチル、メトキシフェネチルアルコール、ベンジルフェノール（Ｃ１３Ｈ１２Ｏ）、ヘキサデカンニトリル、ヘプタデカンニトリル、安息香酸ベンジル、シンメチリン、アジピン酸ビス（２－エチルヘキシル）等が挙げられる。無加圧での接合が一層容易になる観点から、高沸点分散媒が、イソボルニルシクロヘキサノール、トリブチリン、ステアリン酸ブチル及びオクタン酸オクチルからなる群より選択される少なくとも１種を含むことが好ましい。
　高沸点分散媒の含有量は、接合用銅ペーストの全質量を基準として、２質量％以上、２．２質量％以上又は２．４質量％以上であってよく、５０質量％以下、４５質量％以下、４０質量％以下、２０質量％以下、１０質量％以下又は５質量％以下であってもよい。例えば、３００℃以上の沸点を有する化合物の含有量は、接合用銅ペーストの全質量を基準として、２～５０質量％であってよく、２～２０質量％であってよく、２～５質量％であってよい。
　高沸点分散媒の含有量は、分散媒の全質量を基準として、１０～５０質量％であってもよく、２０～４０質量％であってもよく、２５～３５質量％であってもよい。
（その他の成分）
　接合用銅ペーストは、添加剤として、ノニオン系界面活性剤、フッ素系界面活性剤等の濡れ向上剤；表面張力調整剤；アルキルアミン、アルキルカルボン酸等の分散剤；シリコーン油等の消泡剤；無機イオン交換体等のイオントラップ剤；飽和高級アルコールなどを含有することができる。添加剤の含有量は、本発明の効果を阻害しない範囲で適宜調整することができる。
　上述した接合用銅ペーストの粘度は特に限定されないが、スクリーン印刷等の手法、特には自動印刷機の印刷条件への適合の観点から、２５℃における粘度が１００～２５０Ｐａ・ｓであってよく、１００～２００Ｐａ・ｓであってよく、１００～１７０Ｐａ・ｓであってよい。
　接合用銅ペーストの粘度は、ＪＩＳで規格されているソルダーペーストの粘度測定方法（ＪＩＳ　Ｚ　３２８４－１：２０１４）に基づき測定することができ、上記粘度は、粘度計ＴＶ－３３（東機産業（株）製、製品名）と、測定用冶具としてＳＰＰローターを用い、回転数２．５ｒｐｍ、計測時間１４４秒の条件で測定したときの値を示す。
　本実施形態の接合用銅ペーストによれば、充分な接合性を維持しつつ印刷性を向上させることができる。そのため、本実施形態の接合用銅ペーストによれば、スクリーン印刷機等の自動印刷機を用いる量産プロセスによって接合体を効率よく製造することができる。また、本実施形態の接合用銅ペーストは無加圧接合用であってもよい。
＜接合用銅ペーストの調製＞
　接合用銅ペーストは、上述の銅粒子と、分散媒と、場合により含有されるその他の金属粒子及び添加剤とを混合して調製することができる。各成分の混合後に、撹拌処理を行ってもよい。接合用銅ペーストは、分級操作により分散液の最大粒径を調整してもよい。このとき、分散液の最大粒径は２０μｍ以下とすることができ、１０μｍ以下とすることもできる。上記サブマイクロ銅粒子等の金属粒子は、表面処理剤で処理されたものを用いてよい。
　銅粒子として、サブマイクロ銅粒子及びマイクロ銅粒子を用いる場合、接合用銅ペーストは、例えば、以下の方法で調製してよい。まず、分散媒に、必要に応じて分散剤を加えた上で、サブマイクロ銅粒子を混合し、分散処理を行う。次いで、マイクロ銅粒子及び必要に応じてその他の金属粒子を加え、分散処理を行う。サブマイクロ銅粒子とマイクロ銅粒子では分散に適した分散方法及び分散条件が異なる場合がある。一般に、サブマイクロ銅粒子はマイクロ銅粒子よりも分散し難く、サブマイクロ銅粒子を分散させるためには、マイクロ銅粒子を分散させる際に加える強度よりも高い強度が必要である。一方、マイクロ銅粒子は、分散しやすいだけでなく、分散させるために高い強度を加えると変形を生じる場合がある。そのため、上記のような手順とすることで、良好な分散性が得られやすく、接合用銅ペーストの性能をより向上させることができる。
　分散処理は、分散機又は攪拌機を用いて行うことができる。分散機及び攪拌機としては、例えば、石川式攪拌機、シルバーソン攪拌機、キャビテーション攪拌機、自転公転型攪拌装置、超薄膜高速回転式分散機、超音波分散機、ライカイ機、二軸混練機、ビーズミル、ボールミル、三本ロールミル、ホモミキサー、プラネタリーミキサー、超高圧型分散機及び薄層せん断分散機が挙げられる。
　分級操作は、例えば、ろ過、自然沈降及び遠心分離により行うことができる。ろ過用のフィルタとしては、例えば、水櫛、金属メッシュ、メタルフィルター及びナイロンメッシュが挙げられる。
　攪拌処理は、攪拌機を用いて行うことができる。攪拌機としては、例えば、石川式攪拌機、自転公転型攪拌装置、ライカイ機、二軸混練機、三本ロールミル及びプラネタリーミキサーが挙げられる。
＜接合体の製造方法＞
　本実施形態の接合体の製造方法は、第１の部材と、第２の部材と、第１の部材及び第２の部材を接合する接合部と、を備える接合体の製造方法であって、第１の部材及び第２の部材の少なくとも一方の接合面に本実施形態の接合用銅ペーストを印刷し、第１の部材、接合用銅ペースト、及び第２の部材がこの順に積層されている積層構造を有する積層体を用意する第１の工程と、積層体の接合用銅ペーストを焼結する第２の工程と、を備える。
　第１の部材及び第２の部材としては、例えば、ＩＧＢＴ、ダイオード、ショットキーバリヤダイオード、ＭＯＳ－ＦＥＴ、サイリスタ、ロジック、センサー、アナログ集積回路、ＬＥＤ、半導体レーザー、発信器等の半導体素子；リードフレーム；金属板貼付セラミックス基板（例えばＤＢＣ）；ＬＥＤパッケージ等の半導体素子搭載用基材；銅リボン及び金属フレーム等の金属配線；金属ブロック等のブロック体；端子等の給電用部材；放熱板；水冷板などが挙げられる。
　第１の部材及び第２の部材の接合用銅ペーストの焼結体と接する面及びは金属を含んでいてもよい。金属としては、例えば、銅、ニッケル、銀、金、パラジウム、白金、鉛、錫、コバルト等が挙げられる。金属は、１種を単独で使用してもよく、２種以上を組み合わせて使用してもよい。また、焼結体と接する面は、上記金属を含む合金であってもよい。合金に用いられる金属としては、上記金属の他に、亜鉛、マンガン、アルミニウム、ベリリウム、チタン、クロム、鉄、モリブデン等が挙げられる。焼結体と接する面に金属を含む部材としては、例えば、各種金属メッキを有する部材（金属メッキを有するチップ、各種金属メッキを有するリードフレーム等）、ワイヤ、ヒートスプレッダ、金属板が貼り付けられたセラミックス基板、各種金属からなるリードフレーム、銅板、銅箔などが挙げられる。
　部材の接合面に本実施形態の接合用銅ペーストを印刷する方法としては、スクリーン印刷（ステンシル印刷）、転写印刷、オフセット印刷、凸版印刷、凹版印刷、グラビア印刷、ステンシル印刷、ジェット印刷等が挙げられる。また、ディスペンサ（例えば、ジェットディスペンサ、ニードルディスペンサ）、カンマコータ、スリットコータ、ダイコータ、グラビアコータ、スリットコート、バーコータ、アプリケータ、スプレーコータ、スピンコータ、ディップコータ等を用いる方法、ソフトリソグラフィによる方法、粒子堆積法、電着塗装による方法などを用いてもよい。
　接合用銅ペーストの厚さは、１μｍ以上、５μｍ以上、１０μｍ以上、１５μｍ以上、２０μｍ以上又は５０μｍ以上であってよく、３０００μｍ以下、１０００μｍ以下、５００μｍ以下、３００μｍ以下、２５０μｍ以下又は１５０μｍ以下であってよい。例えば、接合用銅ペーストの厚さは、１～１０００μｍであってよく、１０～５００μｍであってもよく、５０～２００μｍであってもよく、１０～３０００μｍであってもよく、１５～５００μｍであってもよく、２０～３００μｍであってもよく、５～５００μｍであってもよく、１０～２５０μｍであってもよく、１５～１５０μｍであってもよい。
　本実施形態においては、量産プロセスの観点から、本実施形態の接合用銅ペーストをスクリーン印刷により印刷することができ、印刷速度向上、マスクの開口の面積拡大等に対応することができる。マスクの開口面積は、例えば、４ｍｍ２以上であってもよく、９ｍｍ２以上であってもよく、２５ｍｍ２以上であってもよく、４９ｍｍ２以上であってもよく、１００ｍｍ２以上であってもよい。
　図１は、スクリーン印刷について説明するための模式図である。図１の（ａ）～（ｄ）は、マスク３２と、スキージ３６を備えるスクリーン印刷機とを用いて、ステージ３５上に配置された第１の部材３０上に、本実施形態の接合用銅ペースト３４を印刷するときの一連のプロセスを示す。このプロセスでは、２つのスキージを用いて往復印刷する。まず、マスク３２の一端にペースト３４を供給する（図１の（ａ））。次に、マスク３２に一方のスキージ３６を所定の印圧で押圧しながら一方向に移動させて、マスク３２の開口部にペースト３４を印刷（コート）する（図１の（ｂ））。ここで、必要に応じてペーストをコート終端部に供給してもよい。次に、コート終端位置にて他方のスキージ３６を所定の印圧で押圧しながら逆方向に移動させて、ペースト３４を印刷（プリント）する（図１の（ｃ））。その後、第１の部材３０をマスク３２から取り外し、印刷が完了する（図１の（ｄ）。こうして、第１の部材３０上に所定の形状を有する接合用銅ペースト３８が印刷される。
　印圧は、例えば、０．０１～０．３ＭＰａとすることができる。印刷速度は、例えば、１５～３００ｍｍ／ｓの範囲で調整することができる。
　本実施形態においては、２つのスキージに代えて、スクレーパーとスキージを取り付け、スクレーパーでペーストをマスクの開口部に充填し、スキージで充填されたペーストを部材上に転写することで印刷を行ってもよい。
　部材上に印刷された接合用銅ペーストは、焼結時の流動及びボイドの発生を抑制する観点から、適宜乾燥させてもよい。乾燥時のガス雰囲気は大気中であってよく、窒素、希ガス等の無酸素雰囲気中であってもよく、水素、ギ酸等の還元雰囲気中であってもよい。乾燥方法は、常温放置（例えば１０～３０℃）による乾燥であってよく、加熱乾燥であってもよく、減圧乾燥であってもよい。加熱乾燥又は減圧乾燥には、例えば、ホットプレート、温風乾燥機、温風加熱炉、窒素乾燥機、赤外線乾燥機、赤外線加熱炉、遠赤外線加熱炉、マイクロ波加熱装置、レーザー加熱装置、電磁加熱装置、ヒーター加熱装置、蒸気加熱炉、熱板プレス装置等を用いることができる。乾燥の温度及び時間は、使用した揮発成分（例えば、１価脂肪族アルコール及び溶剤成分）の種類及び量に合わせて適宜調整してもよい。乾燥条件（乾燥の温度及び時間）は、例えば、５０～１８０℃で１～１２０分間乾燥させる条件であってよい。
　積層体は、一方の部材を他方の部材上に配置する方法によって得ることができる。具体的な方法（例えば、接合用銅ペーストが印刷された第２の部材上に第１の部材を配置する方法）としては、例えば、チップマウンター、フリップチップボンダー、カーボン製又はセラミックス製の位置決め冶具等を用いる方法が挙げられる。
　第２の工程においては、積層体を加熱処理することで、接合用銅ペーストの焼結を行うことができる。これにより接合部となる焼結体が得られる。加熱処理には、例えば、ホットプレート、温風乾燥機、温風加熱炉、窒素乾燥機、赤外線乾燥機、赤外線加熱炉、遠赤外線加熱炉、マイクロ波加熱装置、レーザー加熱装置、電磁加熱装置、ヒーター加熱装置、蒸気加熱炉等を用いることができる。
　焼結時のガス雰囲気は、焼結体、部材（例えば、第１の部材及び第２の部材）の酸化抑制の観点から、無酸素雰囲気であってもよい。焼結時のガス雰囲気は、接合用銅ペースト中の銅粒子の表面酸化物を除去するという観点から、還元雰囲気であってもよい。無酸素雰囲気としては、例えば、窒素、希ガス等の無酸素ガス雰囲気、又は真空が挙げられる。還元雰囲気としては、例えば、純水素ガス雰囲気、フォーミングガスに代表される水素及び窒素の混合ガス雰囲気、ギ酸ガスを含む窒素雰囲気、水素及び希ガスの混合ガス雰囲気、ギ酸ガスを含む希ガス雰囲気等が挙げられる。
　加熱処理時の温度（例えば、到達最高温度）は、部材（例えば、第１の部材及び第２の部材）への熱ダメージを低減できる観点及び歩留まりを向上させる観点から、１７０℃以上、１９０℃以上又は２００℃以上であってよく、２５０℃以下、２５０℃未満、２２５℃以下又は２２５℃未満であってよい。例えば、到達最高温度は、１７０～２５０℃であってもよく、１７０℃以上２５０℃未満であってもよく、１９０～２２５℃であってもよく、１９０℃以上２２５℃未満であってもよく、２００～２２５℃であってもよく、２００℃以上２２５℃未満であってもよい。
　第２の工程において、接合用銅ペーストを無加圧で加熱して焼結してもよい。すなわち、接合用銅ペーストに積層した部材（例えば、第１の部材）による重さのみ、又は積層した部材の重さに加え、０．０１ＭＰａ以下、好ましくは０．００５ＭＰａ以下の圧力を受けた状態で積層体を焼結することができ、このような場合であっても、充分な接合強度を得ることができる。焼結時に受ける圧力が上記範囲内であれば、特別な加圧装置が不要なため歩留まりを損なうこと無く、ボイドの低減、ダイシェア強度及び接続信頼性をより一層向上させることができる。接合用銅ペーストが０．０１ＭＰａ以下の圧力を受ける方法としては、例えば、鉛直方向上側に配置される部材（例えば第１の部材）上に重りを載せる方法等が挙げられる。
　更に、図面を参照して本実施形態の接合体の製造方法について説明する。
　図２は、本実施形態の接合用銅ペーストを用いて製造される接合体の一例を示す模式断面図である。
　図２に示す接合体１００は、第１の部材２と、第２の部材３と、第１の部材２と第２の部材３とを接合する接合部１とを備え、接合部１は上記接合用銅ペーストの焼結体からなる。
　第１の部材２及び第２の部材３については上述したものを挙げることができる。本実施形態の接合用銅ペーストを用いることにより、スクリーン印刷機等の自動印刷機を用いる量産プロセスによっても、充分な接合強度を有する接合体を効率よく製造することができる。
　接合体１００のダイシェア強度は、第１の部材２及び第２の部材３を充分に接合する観点から、１５ＭＰａ以上であってよく、２０ＭＰａ以上であってもよく、２５ＭＰａ以上であってもよく、３０ＭＰａ以上であってもよい。ダイシェア強度は、ユニバーサルボンドテスタ（Ｒｏｙｃｅ　６５０，　Ｒｏｙｃｅ　Ｉｎｓｔｒｕｍｅｎｔｓ社製）又は万能型ボンドテスタ（４０００シリーズ、ＤＡＧＥ社製）等を用いて測定することができる。
　接合用銅ペーストの焼結体１の熱伝導率は、放熱性及び高温化での接続信頼性の観点から、１００Ｗ／（ｍ・Ｋ）以上であってよく、１２０Ｗ／（ｍ・Ｋ）以上であってもよく、１５０Ｗ／（ｍ・Ｋ）以上であってもよい。熱伝導率は、接合用銅ペーストの焼結体の熱拡散率、比熱容量、及び密度から、算出することができる。
　上記接合体１００において、第１の部材２が半導体素子である場合、上記接合体１００は半導体装置となる。得られる半導体装置は充分なダイシェア強度及び接続信頼性を有することができる。
　図３は、本実施形態の接合用銅ペーストを用いて製造される半導体装置の一例を示す模式断面図である。図３に示す半導体装置１１０は、本実施形態に係る接合用銅ペーストの焼結体１１と、リードフレーム１５ａと、リードフレーム１５ｂと、ワイヤ１６と、焼結体１１を介してリードフレーム１５ａ上に接続された半導体素子１８と、これらをモールドするモールドレジン１７と、を備える。半導体素子１８は、ワイヤ１６を介してリードフレーム１５ｂに接続されている。
　本実施形態に係る半導体装置としては、例えば、ダイオード、整流器、サイリスタ、ＭＯＳゲートドライバ、パワースイッチ、パワーＭＯＳＦＥＴ、ＩＧＢＴ、ショットキーダイオード、ファーストリカバリダイオード等のパワーモジュール；発信機；増幅器；高輝度ＬＥＤモジュール；センサーなどが挙げられる。
　図４（図４（ａ）及び図４（ｂ））は、接合体１００の製造方法を説明するための模式断面図である。本実施形態に係る接合体１００の製造方法は、第１の部材２、該第１の部材２の重さが働く方向側に、上記接合用銅ペースト１０、及び第１の部材３がこの順に積層された積層体５０を用意する第１の工程（図４（ａ））と、接合用銅ペースト１０を、第１の部材２の重さを受けた状態、又は第１の部材２の重さ及び０．０１ＭＰａ以下の圧力を受けた状態で、所定の温度で焼結する第２の工程を備える。これにより接合体１００が得られる（図４（ｂ））。第１の部材２の重さが働く方向とは、重力が働く方向ということもできる。
　本実施形態に係る第１の工程及び第２の工程は、上述した第１の工程及び第２の工程と同様に実施することができる。
　本実施形態に係る半導体装置１１０は、上述した接合体１００の製造方法と同様にして製造することができる。すなわち、半導体装置の製造方法は、第１の部材及び第２の部材の少なくとも一方に半導体素子を用い、第１の部材、該第１の部材の重さが働く方向側に、上記接合用銅ペースト、及び第２の部材がこの順に積層された積層体を用意し、接合用銅ペーストを、第１の部材の重さを受けた状態、又は第１の部材の重さ及び０．０１ＭＰａ以下の圧力を受けた状態で、所定の温度で焼結する工程を備える。
　例えば、図５（図５（ａ）～図５（ｃ））に示すように、リードフレーム１５ａ上に接合用銅ペースト２０を印刷し、半導体素子１８を配置して積層体６０を得た後（図５（ａ））、この積層体６０を加熱し、接合用銅ペースト２０を焼結させることにより接合体１０５を得る（図５（ｂ））。次いで、得られた接合体１０５におけるリードフレーム１５ｂと半導体素子１８とをワイヤ１６によって接続し、封止樹脂によりこれらを封止する。以上の工程により半導体装置１１０が得られる（図５（ｃ））。得られる半導体装置１１０は、無加圧での接合を行った場合であっても、充分なダイシェア強度及び接続信頼性を有することができる。本実施形態の半導体装置は、充分な接合力を有し、熱伝導率及び融点が高い銅を含む接合用銅ペーストの焼結体を備えることにより、充分なダイシェア強度を有し、接続信頼性に優れるとともに、パワーサイクル耐性にも優れたものになり得る。また、印刷性及び接合性に優れた本実施形態の接合用銅ペーストが用いられることにより、上記の半導体装置を効率よく製造することができる。
　以上、本実施形態の接合用銅ペーストを用いて製造される接合体及び半導体装置の一例を説明したが、本実施形態の接合用銅ペーストを用いて製造される接合体及び半導体装置は上記実施形態に限られない。本実施形態の接合用銅ペーストを用いて製造される接合体は、例えば、図６及び図８に示す接合体であってもよい。
　図６に示す接合体１２０は、第１の部材２と、第２の部材３と、第３の部材４と、第４の部材５と、第１の部材２と第２の部材３とを接合する上記接合用銅ペーストの焼結体（接合部）１ａと、第１の部材２と第３の部材４とを接合する上記接合用銅ペーストの焼結体（接合部）１ｂと、第３の部材４と第４の部材５とを接合する上記接合用銅ペーストの焼結体（接合部）１ｃと、を備える。
　このような接合体１２０は、例えば、図７（図７（ａ）及び図７（ｂ））に示すように、第３の部材４、該第３の部材４の重さが働く方向側に、第２の接合用銅ペースト１０ｂ、第１の部材２、第１の接合用銅ペースト１０ａ、及び第２の部材３がこの順に積層された積層部分と、第３の部材４、該第３の部材４の重さが働く方向側に、第３の接合用銅ペースト１０ｃ、及び第４の部材５がこの順に積層された積層部分とを有する積層体７０を用意し（図７（ａ））、上記接合体１００の製造方法と同様にして、第１の接合用銅ペースト１０ａ、第２の接合用銅ペースト１０ｂ及び第３の接合用銅ペースト１０ｃを焼結する工程を備える方法で得ることができる（図７（ｂ））。上記方法において、第１の接合用銅ペースト１０ａ、第２の接合用銅ペースト１０ｂ及び第３の接合用銅ペースト１０ｃは本実施形態に係る接合用銅ペーストであり、第１の接合用銅ペースト１０ａが焼結することにより焼結体１ａが得られ、第２の接合用銅ペースト１０ｂが焼結することにより焼結体１ｂが得られ、第３の接合用銅ペースト１０ｃが焼結することにより焼結体１ｃが得られる。
　また、接合体１２０は、例えば、上記接合体１００を得た後、第３の部材４、該第３の部材４の重さが働く方向側に、第２の接合用銅ペースト１０ｂ、及び第１の部材２がこの順に積層された積層部分と、第３の部材４、該第３の部材４の重さが働く方向側に、第３の接合用銅ペースト１０ｃ、及び第４の部材５がこの順に積層された積層部分とを形成し、上記接合体１００の製造方法と同様にして、第２の接合用銅ペースト１０ｂ及び第３の接合用銅ペースト１０ｃを焼結する工程を備える方法で得ることもできる。
　図８に示す接合体１３０は、第１の部材２と、第２の部材３と、第３の部材４と、第４の部材５と、第５の部材６と、第１の部材２と第２の部材３とを接合する上記接合用銅ペーストの焼結体（接合部）１ａと、第３の部材４と第４の部材５とを接合する上記接合用銅ペーストの焼結体（接合部）１ｃと、第１の部材２と第５の部材６とを接合する上記接合用銅ペーストの焼結体（接合部）１ｄと、第３の部材４と第５の部材６とを接合する上記接合用銅ペーストの焼結体（接合部）１ｅと、を備える。
　このような接合体１３０は、例えば、図９（図９（ａ）及び図９（ｂ））に示すように、第３の部材４、該第３の部材４の重さが働く方向側に、第５の接合用銅ペースト１０ｅ、第５の部材６、第４の接合用銅ペースト１０ｄ、第１の部材２、第１の接合用銅ペースト１０ａ、及び第２の部材３がこの順に積層された積層部分と、第３の部材４、該第３の部材４の重さが働く方向側に、第３の接合用銅ペースト１０ｃ、及び第４の部材５がこの順に積層された積層部分とを有する積層体８０を用意し（図９（ａ））、上記接合体１００の製造方法と同様にして、第１の接合用金属ペースト１０ａ、第３の接合用銅ペースト１０ｃ、第４の接合用銅ペースト１０ｄ及び第５の接合用銅ペースト１０ｅを焼結する工程を備える方法で得ることができる（図９（ｂ））。上記方法において、第１の接合用銅ペースト１０ａ、第３の接合用銅ペースト１０ｃ、第４の接合用銅ペースト１０ｄ及び第５の接合用銅ペースト１０ｅは本実施形態に係る接合用銅ペーストであり、第１の接合用銅ペースト１０ａが焼結することにより焼結体１ａが得られ、第３の接合用銅ペースト１０ｃが焼結することにより焼結体１ｃが得られ、第４の接合用銅ペースト１０ｄが焼結することにより焼結体１ｄが得られ、第５の接合用銅ペースト１０ｅが焼結することにより焼結体１ｅが得られる。
　また、接合体１３０は、第３の部材４、該第３の部材４の重さが働く方向側に、第５の接合用銅ペースト１０ｅ、第５の部材６、第４の接合用銅ペースト１０ｄ、第１の部材２、第１の接合用銅ペースト１０ａ、及び第２の部材３がこの順に積層された積層体を用意し、上記接合体１００の製造方法と同様にして、第１の接合用銅ペースト１０ａ、第４の接合用銅ペースト１０ｄ及び第５の接合用銅ペースト１０ｅを焼結した後、第３の部材４、該第３の部材４の重さが働く方向側に、第３の接合用銅ペースト１０ｃ、及び第４の部材５がこの順に積層された積層部分を形成し、上記接合体１００の製造方法と同様にして、第３の接合用銅ペースト１０ｃを焼結する工程を備える方法で得ることもできる。
　また、接合体１３０は、上記接合体１００を得た後、第３の部材４、該第３の部材４の重さが働く方向側に、第５の接合用銅ペースト１０ｅ、第５の部材６、第４の接合用銅ペースト１０ｄ、及び第１の部材２がこの順に積層された積層部分と、第３の部材４、該第３の部材４の重さが働く方向側に、第３の接合用銅ペースト１０ｃ、及び第４の部材５がこの順に積層された積層部分とを形成し、上記接合体１００の製造方法と同様にして、第３の接合用銅ペースト１０ｃ、第４の接合用銅ペースト１０ｄ及び第５の接合用銅ペースト１０ｅを焼結する工程を備える方法で得ることもできる。
　上記変形例において、第３の部材４、第４の部材５及び第５の部材６の例としては、第２の部材３の例と同一である。また、第３の部材４、第４の部材５及び第５の部材６の接合用銅ペーストの焼結体と接する面は金属を含んでいていてもよい。含みうる金属の例は、第１の部材及び第２の部材が接合用銅ペーストの焼結体と接する面に含みうる金属の例と同一である。また、上記変形例において用いる第１の接合用銅ペースト１０ａ、第２の接合用銅ペースト１０ｂ、第３の接合用銅ペースト１０ｃ、第４の接合用銅ペースト１０ｄ、第５の接合用銅ペースト１０ｅは、それぞれ同一であっても異なっていてもよい。
　以下、実施例及び比較例によって、本発明をさらに具体的に説明するが、本発明は以下の実施例に限定されるものではない。
＜接合用銅ペーストの調製＞
（実施例１）
　サブマイクロ銅粒子を含む材料としてＣＨ－０２００（三井金属鉱業（株）製、製品名、５０％体積平均粒径：０．３μｍ）６０．７質量部、ジヒドロターピネオール（日本テルペン化学（株）製）８．０質量部、トリブチリン（沸点：３０５℃、富士フィルム和光純薬（株）製）３．６質量部、及びファインオキソコール－１８０Ｔ（富士フィルム和光純薬（株）製）０．４質量部を、２０００ｒｐｍ、１分間の条件で株式会社シンキー製攪拌機（商品名：「あわとり練太郎　ＡＲＥ－３１０」、以下同様。）にて混合した。その後、３本ロールミルで１０回分散処理を行い、混合物を得た。
　分散処理により得た混合物をポリエチレン製の容器に移した後、フレーク状マイクロ銅粒子を含む材料として３Ｌ３Ｎ（三井金属鉱業（株）製、製品名、５０％体積平均粒径：７μｍ）２７．１質量部を容器に加え、２０００ｒｐｍ、１分間の条件で株式会社シンキー製攪拌機にて混合した。その後、３本ロールミルで５回分散処理を行い、接合用銅ペーストを得た。
（実施例２及び参考例１）
　実施例２は、実施例１におけるペーストの溶媒量を減らして、金属粒子濃度を８９質量％に調整した。参考例１は、接合用銅ペーストの組成を表１に示す組成（数値の単位は質量部）に変更したこと以外は、実施例１と同様にして接合用銅ペーストを調製した。
＜接合用銅ペーストの評価＞
　上記で得られた接合用銅ペーストについて、下記の方法に従って、粘度、印刷性、及び接合性の評価を行った。粘度の結果を表１に示す。
（粘度）
　接合用銅ペーストの粘度は、ＪＩＳで規格されているソルダーペーストの粘度測定方法（ＪＩＳ　Ｚ　３２８４－１：２０１４）に準拠し、粘度計ＴＶ－３３（東機産業（株）製、製品名）と、測定用冶具としてＳＰＰローターを用い、回転数２．５ｒｐｍ、計測時間１４４秒の条件で測定した。
（印刷性）
　銅板上に、下記の条件でスクリーン印刷機による印刷を行い、印刷性を評価した。なお、開口サイズは、３ｍｍ□、５ｍｍ□、７ｍｍ□、及び１０ｍｍ□とした。
　銅板上に、各印刷形状（３ｍｍ□、５ｍｍ□、７ｍｍ□、及び１０ｍｍ□）の開口を有するステンレス製のメタルマスク（厚さ：２００μｍ）を載せ、メタルスキージを備えるステンシル印刷により、往路：速度１５０ｍｍ／ｓ、印圧０．２ＭＰａ、復路：１００ｍｍ／ｓ、印圧０．１ＭＰａの条件で接合用銅ペーストを印刷した。
　実施例１及び２では、全ての開口サイズで良好に印刷できた。参考例１では、印刷領域中に開口エッジ部の欠落と印刷面の荒れが見られた。
（接合性）
　接合用銅ペーストの接合性を、下記の方法で作製した接合体の接合面積率（％）により評価した。
＜接合体の作製＞
　銅板上に、各印刷形状（３ｍｍ□、５ｍｍ□、７ｍｍ□、及び１０ｍｍ□）の開口を有するステンレス製のメタルマスク（厚さ：２００μｍ）を載せ、メタルスキージを用いたステンシル印刷により、往路：速度１５０ｍｍ／ｓ、印圧０．２ＭＰａ、復路：１００ｍｍ／ｓ、印圧０．１ＭＰａの条件で接合用銅ペーストを印刷した。印刷した銅ペーストに、Ｎｉ層が形成されたＳｉチップを載せ、ホットプレート（アズワン製、製品名「ＥＣ－１２００Ｎ」）を用い、６０℃にて５分間又は１０分間の乾燥を行った。次に、チップを載せたサンプルをチューブ炉（株式会社アールデック製）にセットし、アルゴンガスを３Ｌ／ｍｉｎ、５分間流して置換した。その後、水素ガスを５００ｍＬ／ｍｉｎで流し、３０分間で接合温度まで昇温した。昇温後、水素ガスを流しながら２２５℃で６０分保持した後、２００℃まで１５分間かけて冷却した。最後にアルゴンガスを０．３Ｌ／ｍｉｎで流しながら、チューブ炉の外側からエアブローで強制冷却してサンプル温度が６０℃以下になってから、サンプルを空気中に取り出した。
＜接合面積率＞
　接合体のサンプルについて、超音波探傷装置（インサイト（株）製、Ｉｎｓｉｇｈｔ－３００）により分析し、接合部の超音波探傷像（ＳＡＴ像）を得た。得られたＳＡＴ像を二値化処理し、チップ面積に対する接合面積率（ａｒｅａ％）を算出した。
　実施例１及び２では、全ての開口サイズで接合面積率が９９％以上であった。
Figure JPOXMLDOC01-appb-T000001
　表中の各成分の詳細は下記のとおりである。
（銅粒子）
サブマイクロ銅粒子Ａ：ＣＨ－０２００（三井金属鉱業（株）製、製品名、５０％体積平均粒径：０．３μｍ）
マイクロ銅粒子Ａ：３Ｌ３Ｎ（福田金属箔粉工業（株）製、製品名、５０％体積平均粒径：７μｍ）
（その他の金属粒子）
亜鉛粒子Ａ：Ｚｉｎｃ　ｐｏｗｄｅｒ（Ａｌｆａ　Ａｅｓａｒ社製、製品名、５０％体積平均粒径：４μｍ）
（分散媒）
ジヒドロターピネオール：日本テルペン化学（株）製、製品名、沸点２０８℃
ターピネオールＣ：日本テルペン化学（株）製、製品名、沸点２２０℃
トリブチリン：富士フィルム和光純薬（株）製、製品名、沸点３０５℃
（添加剤）
添加剤Ａ：ファインオキソコール－１８０Ｔ（富士フィルム和光純薬（株）製、イソオクタデカノール）
　表１に示されるように、実施例１及び２の接合用銅ペーストは、自動印刷を想定した印刷条件において、開口サイズ３～１０ｍｍ□で良好に印刷することができ、充分な接合性を達成できることが確認された。ジヒドロターピネオールは、ターピネオールの分子構造に含まれる二重結合を水素添加して一重結合にしたものであり、分子構造や特性はターピネオールと非常に似ていると思われるところ、銅ペーストの粘度を大きく低減することができ、充分な接合性が得られることは予想外の効果といえる。
１，１ａ，１ｂ，１ｃ，１ｄ，１ｅ，１１…接合用銅ペーストの焼結体（接合部）、２…第１の部材、３…第２の部材、１０，１０ａ，１０ｂ，１０ｃ，１０ｄ，１０ｅ，２０…接合用銅ペースト、１５ａ，１５ｂ…リードフレーム、１６…ワイヤ、１７…モールドレジン、１８…半導体素子、３０…第１の部材、３２…マスク、３４，３８…接合用銅ペースト、３５…ステージ、３６…スキージ、５０，６０，７０，８０…積層体、１００，１０５，１２０，１３０…接合体、１１０…半導体装置。

Claims (15)

  1. 　金属粒子と、分散媒と、を含有し、
    　前記金属粒子として、銅粒子を含み、
    　前記分散媒として、ジヒドロターピネオールを含む、接合用銅ペースト。
  2. 　前記金属粒子の含有量が、接合用銅ペースト全量を基準として、８５～９８質量％である、請求項１に記載の接合用銅ペースト。
  3. 　前記分散媒として、沸点が３００℃以上である化合物を更に含む、請求項１又は２に記載の接合用銅ペースト。
  4. 　２５℃における粘度が１００～２００Ｐａ・ｓである、請求項１～３のいずれか一項に記載の接合用銅ペースト。
  5. 　前記銅粒子の含有量が、前記金属粒子の全質量を基準として、８０～１００質量％である、請求項１～４のいずれか一項に記載の接合用銅ペースト。
  6. 　スクリーン印刷用である、請求項１～５のいずれか一項に記載の接合用銅ペースト。
  7. 　前記銅粒子として、体積平均粒径が０．１２～０．８μｍであるサブマイクロ銅粒子と、最大径が２～５０μｍであり、アスペクト比が３．０以上であるフレーク状のマイクロ銅粒子と、を含む、請求項１～６のいずれか一項に記載の接合用銅ペースト。
  8. 　前記サブマイクロ銅粒子の含有量は、前記銅粒子の全質量を基準として、３０～９０質量％であり、
    　前記マイクロ銅粒子の含有量は、前記銅粒子の全質量を基準として、１０～７０質量％である、請求項７に記載の接合用銅ペースト。
  9. 　無加圧接合用である、請求項１～８のいずれか一項に記載の接合用銅ペースト。
  10. 　第１の部材と、第２の部材と、前記第１の部材及び前記第２の部材を接合する接合部と、を備える接合体の製造方法であって、
    　前記第１の部材及び前記第２の部材の少なくとも一方の接合面に請求項１～８のいずれか一項に記載の接合用銅ペーストを印刷し、前記第１の部材、前記接合用銅ペースト、及び前記第２の部材がこの順に積層されている積層構造を有する積層体を用意する第１の工程と、
    　前記積層体の前記接合用銅ペーストを焼結する第２の工程と、
    を備える、接合体の製造方法。
  11. 　前記印刷がスクリーン印刷である、請求項１０に記載の接合体の製造方法。
  12. 　前記第２の工程において、前記接合用銅ペーストを無加圧で加熱して焼結する、請求項１０又は１１に記載の接合体の製造方法。
  13. 　前記第１の部材及び前記第２の部材の少なくとも一方が半導体素子である、請求項１０～１２のいずれか一項に記載の接合体の製造方法。
  14. 　第１の部材、第２の部材、及び、第１の部材と第２の部材とを接合する接合部、を備え、
    　前記接合部が、請求項１～８のいずれか一項に記載の接合用銅ペーストの焼結体からなる、接合体。
  15. 　前記第１の部材及び前記第２の部材の少なくとも一方が半導体素子である、請求項１４に記載の接合体。
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