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WO2004027787A1 - Composition conductrice pour la connexion electrique d'un dispositif electronique et dispositif electronique - Google Patents

Composition conductrice pour la connexion electrique d'un dispositif electronique et dispositif electronique Download PDF

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Publication number
WO2004027787A1
WO2004027787A1 PCT/JP2003/012011 JP0312011W WO2004027787A1 WO 2004027787 A1 WO2004027787 A1 WO 2004027787A1 JP 0312011 W JP0312011 W JP 0312011W WO 2004027787 A1 WO2004027787 A1 WO 2004027787A1
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WO
WIPO (PCT)
Prior art keywords
metal
conductive
particles
composition
powder
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2003/012011
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English (en)
Japanese (ja)
Inventor
Hirotaka Ogawa
Isao Suzuki
Keisuke Abe
Kentarou Tsunozaki
Yasuhiro Sanada
Hisao Inokuma
Masako Kawamoto
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Noda Screen Co Ltd
AGC Inc
Original Assignee
Asahi Glass Co Ltd
Noda Screen Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Asahi Glass Co Ltd, Noda Screen Co Ltd filed Critical Asahi Glass Co Ltd
Priority to AU2003266547A priority Critical patent/AU2003266547A1/en
Publication of WO2004027787A1 publication Critical patent/WO2004027787A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/09—Use of materials for the conductive, e.g. metallic pattern
    • H05K1/092—Dispersed materials, e.g. conductive pastes or inks
    • H05K1/095—Dispersed materials, e.g. conductive pastes or inks for polymer thick films, i.e. having a permanent organic polymeric binder

Definitions

  • the present invention relates to a conductive composition for electrically connecting an electronic device and an electronic device.
  • the present invention relates to a conductive composition for electrically connecting electronic devices and an electronic device using the conductive composition.
  • a metal-containing composition sometimes called a conductive base
  • conductive particles such as silver powder and a resin
  • a method of forming an electric circuit (wiring conductor) such as a wiring board and an electronic component and a contact hole filling member is generally known. (See, for example, “Electronic Materials,” Industrial Research Council, October 1998, p. 42-46.)
  • the metal-containing composition is composed of a conductive filler which is a powder, a resin, a diluent, and the like. If the ratio of the conductive filler is excessively increased, the amount of the resin and the diluent decreases, and the metal-containing composition decreases. The composition itself loses fluidity or becomes powdery, making it difficult to apply, print and fill.
  • the flat-tree-shaped conductive filler has a lower density than the spherical conductive filler, the additive concentration in the metal-containing composition is lower than that of the spherical conductive filler.
  • the circuit forming portion becomes finer, the fluidity requirement for the metal-containing composition itself becomes higher, and such a drawback has become more remarkable with the trend of miniaturization of electronic devices.
  • it is desired to suppress deterioration that is, to improve the durability of a circuit made of a conductive composition obtained by subjecting a metal-containing composition to heat treatment or the like and an electrical connection site in a contact hole.
  • the thermal expansion coefficient of the constituent material in the conductive composition is not uniform, and the thermal expansion is repeated as the Z contraction is repeated. It is known that a fine crack is generated in a connection portion and a conductive path is cut.
  • the conductive composition solidifies and connects the conductive fillers with a resin, and a conductive path is formed by physical contact between the conductive fillers.
  • Thermal expansion coefficient of copper and silver as the material of the representative conductive filler are each 17X 10- 6 ° C one 1, 19X 10- 6 ° ⁇ -], the thermal expansion coefficient of the epoxy resins which are commonly used There considering that a 50 X 1 0- 6 ⁇ 1 0 0 X 1 0- 6 ° C- 1, to human one preparative cycles of thermal expansion Z contraction, prior to rely only on physical contact of the filler It can be said that there is essentially a limit in improving the durability of a metal-containing composition.
  • the present invention relates to a conductive composition for electrical connection of electronic devices, which is excellent in conductivity and durability, and is also excellent in applicability, printability, and filling property, and an electrically connected portion of the conductive composition. Further objects and advantages of the invention, which are to provide a highly reliable electronic device applied to the present invention, will be apparent from the following description.
  • the first aspect of the present invention relates to a metal particle powder having an average particle size of 2 Onm or less (hereinafter, “metal particle powder having an average particle size of 2 Onm or less” is also referred to as “metal particle powder A”).
  • Metal powder having a particle size of 50 nm or more and 2000 nm or less (hereinafter, “metal particle powder having an average particle diameter of 50 nm or more and 200 Onm or less” is also referred to as “metal particle powder B”)
  • Metals containing conductive particle powder having an average particle size of more than 2000 nm and not more than 20 hereinafter, “conductive particle powder having an average particle size of more than 2000 nm and not more than 20” is also referred to as “conductive particle powder C”)
  • the concentration of the metal particle powder A in the metal-containing composition is a mass%
  • the concentration of the metal particle powder B is b mass%
  • the concentration of the conductive particle powder C is c mass%. If a: b is between 3:97 to 90:10
  • a third aspect of the present invention is directed to a third aspect of the present invention, which includes metal particles, a resin, and, in some cases, conductive particles, and has a particle size of 20 nm or less based on the total amount of the metal particles and the conductive particles.
  • the mass ratio between the metal particles having a diameter of 50 nm or more and 200 nm or less is 3:97 to 90:10 by mass ratio, and the metal particles having a particle size of 20 nm or less and the particles are present.
  • Metal particles having a diameter of 50 nm or more and 200 nm or less are contained in a total amount of 60 to 100% by mass, and conductive particles having a diameter of more than 200 nm and 20 or less are 40 to 100%. What is claimed is: 1.
  • a method for measuring solid particles present in the metal-containing composition by dynamic light scattering Of the particle size distribution below 20 nm and 50 nm Energy is applied to a metal-containing composition in which a peak exists in the upper particle size region of 2000 nm or less, and in some cases, a peak exists in a particle size region of more than 2000 nm and 20 zm or less.
  • a conductive composition for electrical connection of electronic devices
  • At least one arbitrarily selected in 0. 1 mm 2 cross-section of the conductive composition needle-like shape composed of a metal or metals and electrically conductive particles, dendritic shape, Igagu Ri shapes and irregular
  • At least one new shape selected from the group consisting of connected shapes is newly generated,
  • the conductive particle powder C When the conductive particle powder C is present, the conductive particle powder C
  • Metal particles with a particle size of 20 nm or less and metals with a particle size of 50 nm or more and 2000 nm or less The group consisting of Ag, Au, u, Pd, Pt, Re, Os, Ir, Cu, Ni, Sn, A1, Zn, In, Co, W, and Mo, respectively At least one of metal particles of at least one element selected from the group consisting of metal particles and alloy particles containing the element,
  • At least one kind of conductive carbon compound selected from the group consisting of graphite, a carbon compound having a graphite structure, and a carbon nano tube;
  • the conductive composition according to the above aspect 3 or 4 comprising at least one of the following.
  • the resin is an epoxy-based curable resin, a phenol-based curable resin, a melamine-based curable resin, a silicone-based curable resin, an acrylic resin, polyethylene, polystyrene, polypropylene, or polychlorinated resin.
  • the conductive composition according to any one of the above aspects 1 to 7 is applied to at least one kind of electrical connection site selected from the group consisting of a via hole, a through hole, and a wiring.
  • Electronic device BRIEF DESCRIPTION OF THE FIGURES
  • FIG. 1 is a model diagram illustrating a needle-shaped metal composite.
  • FIG. 2 is another model diagram illustrating a needle-shaped metal composite.
  • FIG. 3 is another model diagram illustrating a needle-shaped metal composite.
  • FIG. 4 is another model diagram illustrating a needle-shaped metal composite.
  • FIG. 5 is another model diagram illustrating a needle-shaped metal composite.
  • FIG. 6 is another model diagram illustrating a needle-shaped metal composite.
  • FIG. 7 is a model diagram illustrating a tree-shaped metal combination.
  • FIG. 8 is another model diagram illustrating a tree-shaped metal combination.
  • FIG. 9 is a model diagram illustrating a ragged metal combination.
  • FIG. 10 is another model diagram illustrating a ragged metal combination.
  • FIG. 11 is another model diagram illustrating a ragged metal combination.
  • FIG. 12 is another model diagram illustrating a ragged metal combination.
  • FIG. 13 is another model diagram illustrating a metal joint having an irregular connection shape.
  • FIG. 14 is a particle size distribution diagram of Ag fine particle powder as metal particle powder A.
  • FIG. 15 is a photograph of a transmission electron microscope image of Ag fine particle powder as metal particle powder A.
  • Figure 16 shows peaks in the particle size range below 20 nm, the particle size range from 500 nm to 200 nm, and the particle size range above 200 nm to 20 nm.
  • FIG. 4 is a particle size distribution diagram showing the appearance of the process.
  • FIG. 17 is a cross-sectional photograph of the conductive composition for electrical connection of an electronic device according to the present invention.
  • FIG. 18 is another cross-sectional photograph of the conductive composition for electrical connection of an electronic device according to the present invention.
  • FIG. 19 is another cross-sectional photograph of the conductive composition for electrical connection of an electronic device according to the present invention.
  • FIG. 20 is another cross-sectional photograph of the conductive composition for electrical connection of an electronic device according to the present invention.
  • FIG. 21 is a model diagram showing an example of use of the conductive composition for electrical connection of an electronic device according to the present invention.
  • FIG. 22 is a model diagram showing another usage example of the conductive composition for electrical connection of an electronic device according to the present invention.
  • FIG. 23 is a model diagram showing another example of use of the conductive composition for electrical connection of an electronic device according to the present invention.
  • FIG. 24 is a model diagram showing another usage example of the conductive composition for electrical connection of an electronic device according to the present invention.
  • FIG. 25 is a model diagram showing another usage example of the conductive composition for electrical connection of an electronic device according to the present invention.
  • FIG. 26 is a model diagram showing another usage example of the conductive composition for electrical connection of an electronic device according to the present invention.
  • FIG. 27 is a side view model diagram of a substrate for evaluation of a cured composition.
  • FIG. 28 is a plan model diagram of a substrate for evaluation of a cured composition.
  • FIG. 29 is another cross-sectional photograph of the conductive composition for electrical connection of an electronic device according to the present invention.
  • FIG. 30 is another cross-sectional photograph of the conductive composition for electrical connection of an electronic device according to the present invention.
  • the metal-containing composition used in the present invention is a paste-like composition containing metal particle powder A, metal particle powder B, and resin.
  • the metal-containing composition used in the present invention can be a paste having an appropriate viscosity, and can be sufficiently filled in a fine via hole having a diameter of 50 im or less. Fine circuit wiring with a line width of 20 m or less Becomes possible. With respect to the viscosity of the metal-containing composition, for example, a paste of 10 to 2000 dPa's having good handleability, coatability, printability, and filling property can be easily produced.
  • the metal-containing composition used in the present invention after filling the via hole and forming the wiring pattern, imparts energy to cure the curable resin, and if it is a thermoplastic resin, softens or melts it to form a conductive material.
  • surface melting occurs in metal particles with a particle size of 20 nm or less. It should be noted that since fine particles of this level have a sharp particle size distribution, there is no inconvenience even if it is considered that the metal particle powder A actually causes surface melting.
  • the resin contained in the metal-containing composition mainly, a curable resin or a combination of a curable resin and a thermoplastic resin has been described, but the resin contained in the metal-containing composition according to the present invention is included.
  • the resin may be a thermoplastic resin alone.
  • "cured” is replaced with “solidified” and "cured composition” is replaced with “solidified composition” within a range not contrary to the gist of the present invention. .
  • the surface melting of metal particles is caused by anomalous lattice vibration of the particle surface elements.
  • the surface atomic ratio (the ratio of the atoms present on the particle surface to the total number of atoms in the whole particle) is calculated to be 20% for a particle with a diameter of 10 nm, 10% for a particle with a diameter of 20 nm, and 7 O nm for a particle with a diameter of 20 nm. Less than 3% for particles. Due to this effect, the melting point of the bulk material is 961 ° C for silver, but surface melting is observed at around 160 ° C for particles with a diameter of 10 nm. (
  • the metal-containing composition does not contain the metal particle powder B and the metal-containing composition is prepared only with the metal particle powder A and the resin, the metal particles present therein are fine, The connection between the particles is often insufficient.
  • a paste-like metal-containing composition having high fluidity is prepared with metal particle powder A and a solvent in order to facilitate metal bonding between particles, the connection between particles is improved, It is necessary to heat the solvent to a temperature higher than the boiling point, which increases the process cost and greatly reduces the quality of other electronic components. Such behavior can be easily observed, for example, with fine Ag particles.
  • the particles of the metal particle powder B in the vicinity of the fine metal particles, the surface itself of the fine metal particles is melted, and then at the stage of bonding to the metal particle powder B, the combined body itself Is still not sufficiently large, so the surface energy is not stable, and it is thought that self-growth can be continued while entraining particles existing in the vicinity.
  • the shape in the cross section is different from the shape in the metal-containing composition.
  • needle-like shapes, tree-like shapes, burrow shapes, and irregularly-connected shapes are the results of connection between particles. Therefore, even when subjected to a heat cycle, it is possible to prevent the occurrence of minute cracks in the electrical connection portion and the breakage of the conductive path.
  • the needle-like shape means a rod-like or needle-like shape 1 as illustrated in FIGS. Some are wide as shown in Figs.
  • the dendritic shape means a bent rod-like or needle-like shape, or a shape 2 branched into three or more as illustrated in Figs.
  • the burrow shape 3 refers to a shape in which one or more rod-shaped or needle-shaped shapes 1 protrude from a solid shape. It should be noted that voids 4 may be present in the above-mentioned drawings.
  • the irregular connection shape 5 is considered to be a shape formed by connecting needle-like shapes, tree-like shapes, and burrow shapes.
  • the protruding shape in the needle shape, the dendritic bent shape or the branch shape, and the protruding shape in the burrow shape has an aspect ratio of 3 or more. As shown in FIGS. 1 to 12, the ratio between L1 and W1 is an example of the aspect ratio.
  • the length (L) is not uniform, the value of the largest aspect ratio is used for the aspect ratio. If there are multiple lengths (L) such as Ll and L2 in Fig. 8, the larger one is adopted.
  • the metal-containing composition used in the above may further contain conductive particle powder C.
  • the metal binder formed by the self-growth mechanism of the metal particle powder A and the metal particle powder B causes the particles of the conductive particle powder C Can be connected, which is preferable in terms of forming a conductive path.
  • the conductive particle powder C itself does not need to grow by itself, metals, conductive oxides, and conductive compounds can be used.
  • the particle size distribution and the average particle size are determined by a dynamic light scattering measuring method.
  • the electrical connection for the conductive composition of the electronic device configurations at least one of the cross-section of 0. 1 mm 2 arbitrarily selected, as described above, by the metal or metals and electrically conductive particles
  • At least one new shape selected from the group consisting of a needle-like shape, a tree-like shape, a burrow shape, and an irregular connection shape is newly generated.
  • the conductive composition for electrical connection of electronic devices obtained by applying energy such as heat treatment to the metal-containing composition used in the present invention has excellent conductivity and durability. .
  • the concentration of the metal particle powder A in the metal-containing composition is a mass%
  • the concentration of the metal particle powder B is b mass%
  • the concentration of the conductive particle powder C is c mass%
  • a: b is 3:97.
  • (a + b): c is between 100: 0 and 60:40, and that 50.ltoreq.
  • a + b): c force s, 100: 0 to 60: 40, the self-growth tends to occur easily, and if c is not 0 (zero), the connection between metal particles is promoted.
  • a: b is between 3:97 and 90:10, needle-like, tree-like, ragged, irregularly connected shapes, etc. will grow. 50 ⁇ (a + b + c) If it is ⁇ 95, the number of needle-like, tree-like, scrambled, irregularly connected shapes, etc. is large, and it is easy to secure conductivity. When the above conditions are satisfied, excellent conductivity, durability, coatability, printability, and filling properties, which are characteristics of the conductive composition for electrical connection of an electronic device according to the present invention, are more highly exhibited. .
  • the metal particle powder A and the metal particle powder B are respectively Ag, Au, Ru, Pd, Pt, Re, Os, Ir, Cu, Ni, Sn, A1, Zn, In, Co, W And metal particles of at least one element selected from the group consisting of It is preferable to include at least one of alloy particles containing:
  • the electrical resistivity (resistivity) of these elements is as follows: Ag: 1.63 / ⁇ cm, Au: 2.2 ⁇ cm, Ru: 7.37 cm, ⁇ d: 10.55 / i ⁇ cm, ⁇ t: 10.42 Qcm, Re: 18.8.7 ⁇ , Os: 9.13 ⁇ ⁇ cm, Ir: 5.07 ⁇ cm, Cu: 1.6 9 ⁇ ⁇ , N i: 30.6 x ⁇ cm, S n: 12.6 ⁇ ⁇ cm, A 1: 2.67 ⁇ cm, Z n: 5.96 ⁇ cm, I n: 9 O zQ cm, Co: 6.24 Q cm, W: 5.5 ⁇ cm, Mo: 5.7 ⁇ cm, all of which are available.
  • metal particle powder A and the metal particle powder B according to the present invention are connected and self-growth between the metal particles in a paste-like metal-containing composition having fluidity when energy is applied.
  • the metal particle powder A and the metal particle powder B may be any combination of the same metal atomic species or a metal that does not hinder self-growth.
  • the combination forms a solid solution entirely.
  • there are combinations such as Ag-Au, Ag-Pd, Pd-Au, Au-Cu, and Ru_Re.
  • the combination does not form a solid solution, it is preferable to use a combination of metal species that causes surface melting on the metal particles of the metal particle powder A and easily bonds to the surface of the metal particles of the metal particle powder B.
  • the electrical resistivity may be worse than that of a single metal depending on the combination of metals, but it is possible to easily select an appropriate one through experiments and the like.
  • the conductive particle powder C according to the present invention means powder of conductive particles. It is preferable that the particles have an electrical resistivity of 150 0 ⁇ cm or less. Therefore, particles of a substance other than metal particles also belong to the category of conductive particles.
  • Examples of the conductive particle powder C include Ag, Au, Ru, Pd, Pt, Re, Os, Ir, Cu, Ni, Sn, Al, Zn, In, Co, W and Metal particles of at least one element selected from the group consisting of Mo, alloy particles containing the element, and a group consisting of In, Ru, Re, Os, Ir, and Sn And at least one conductive material selected from the group consisting of graphite, a carbon compound having a graphite structure, and a carbon nanotube. It is preferable to include at least one of carbon compounds.
  • graphite is a hexagonal hexagonal plate-like flat crystal with a six-membered carbon ring forming a layered structure, and the electrical resistivity in the layer plane is about 40 ⁇ cm. , Available.
  • the conductive carbons that are generally sold there are carbons in which a part of the graphite structure is formed in the crystal. Available.
  • the carbon nanotube has a shape in which the graphite sheet is formed into a cylindrical shape, and a boundary condition occurs structurally, and t ub e (n, m) is displayed as a chiral vector.
  • the particles are bonded to each other in the cured product irrespective of the crosslinking effect of the resin. , The bond is strong and the conductivity is high. Also, unlike the form of the particles that were previously present in the metal-containing composition, the bonded form is in a state in which the aspect ratio has changed greatly, and it is easy to form a network with each other. It also contributes to structural stability during heat cycles.
  • the effect equivalent to that of the metal-containing composition for electrical connection of an electronic device comprising the metal particle powder A and the metal particle powder B and, in some cases, the conductive particle powder C according to the present invention is the same as that of the particles.
  • metal particles and a resin, and in some cases, conductive particles are included, and the metal particles having a particle size of 20 nm or less and the particle size are not more than the total amount of the metal particles and the conductive particles.
  • the mass ratio between the metal particles of 50 nm or more and 200 nm or less is 3:97 to 90:10 by mass ratio, and the metal particles having a particle size of 20 nm or less and the particle size are 20 nm or less.
  • the metal or metal At least one new shape selected from the group consisting of a needle-like shape, a dendritic shape, a scrambled shape, and an irregularly-connected shape constituted by conductive particles can be newly generated.
  • the mass ratio of the metal particles having a particle size of 20 nm or less to the metal particles having a particle size of 50 nm or more and 200 nm or less is 3: 9 with respect to the total amount of the metal particles and the conductive particles. 7-9 When the ratio is between 0 and 10, needle-like, tree-like, ragged, irregularly connected shapes, etc. tend to grow, and metal particles having a particle size of 20 nm or less and particles having a particle size of 50 nm or more are 20 nm or more.
  • the metal particles having a size of 200 nm or less When a total of 60% by mass or more of the metal particles having a size of 200 nm or less is included, self-growth of the metal particles easily occurs, and the conductive particles having a size of more than 200 nm and 20 m or less are reduced to 40% or less. This is because if the content is less than the percentage by mass, the connection between the metal particles is promoted.
  • the total of the metal particles having a particle size of 20 nm or less, the metal particles having a particle size of 50 nm or more and 200 nm or less, and the conductive particles having a particle size of 200 nm or more and 20 m or less is:
  • the content is preferably 50 to 95% by mass in the metal-containing composition.
  • the conductive composition for electrical connection of the electronic device according to the present invention has excellent conductivity, durability, coating properties, printability, and filling properties, which are highly developed. You.
  • the particle size range of 20 nm or less and the particle size range of 50 nm to 200 nm A similar effect can be achieved even with a metal-containing composition in which a peak is present in each case, and in some cases, a peak is present in a particle size region of more than 2000 nm and not more than 20 m.
  • the metal or metal in electrically connecting the conductive composition of the electron Debaisu obtained in such a case at least one 0. 1 mm 2 of a cross section arbitrarily selected, as described above, the metal or metal At least one new shape selected from the group consisting of a needle-like shape, a dendritic shape, a scrambled shape, and an irregularly-connected shape constituted by conductive particles can be newly generated.
  • the particles existing in the particle diameter region of 20 nm or less and the particle diameter region of 500 nm or more and 200 nm or less are substantially made of metal particles.
  • the particle size distribution of the solid particles present in the metal-containing composition refers to the case where other solid particles other than metal particles and conductive particles are present.
  • the metal particles having a particle size of 20 nm or less and the particle size of 50 nm or more are used.
  • the conductive particles are Ag, Au, Ru, Pd, Pt, e, Os, Ir, Cu, Ni, Sn, A1, Zn, In, Co, "W And Mo, selected from the group consisting of metal particles of at least one element selected from the group consisting of Mo, alloy particles containing the element, and In, Ru, Re, ⁇ s, Ir, Sn. Contains at least one of the specified elements It is preferable that the conductive oxide particles include at least one of conductive oxide particles and at least one conductive carbon compound selected from the group consisting of graphite, a carbon compound having a graphite structure, and a carbon nanotube. Preferred.
  • At least one method of heating, ultraviolet irradiation, X-ray irradiation, electron beam irradiation, and ultrasonic irradiation is used.
  • a heating method a method such as hot air heating or heat radiation can be used. The heating temperature and the processing time can be appropriately determined based on the properties actually required.
  • a low-pressure UV lamp having a main wavelength of 254 nm or a high-pressure UV lamp having a main wavelength of 365 nm can be used.
  • Short wave in energy Although the long ultraviolet light has high energy, it is preferable to appropriately determine it in consideration of the irradiation time and the like.
  • a curing initiator that reacts with the ultraviolet light and cures the ultraviolet light can be added to the metal-containing composition.
  • X-rays and electron beams are also high-energy radiation, and can be used from the viewpoint of imparting energy.
  • an electron beam is preferable because heat energy can be applied to only the irradiated portion in a short time.
  • ultrasonic irradiation bubbles can be generated in the uncured metal-containing composition, and the bubbles can be cured using thermal energy at the time of cleavage.
  • the resin used in the present invention may be any resin that imparts fluidity to the metal-containing composition before the metal-containing composition is cured, and is in a state where the resins are solidified at the stage of curing.
  • a curable resin such as a resin is preferable, but a thermoplastic resin or the like may be used in combination or alone.
  • Other resins may be contained as long as they do not contradict the spirit of the present invention.
  • the resin itself is a solid, it may be dissolved in an organic solvent or a reactive diluent.
  • the curable resin at least one curable resin selected from the group consisting of an epoxy curable resin, a phenol curable resin, a melamine curable resin, and a silicone curable resin is preferable.
  • the thermoplastic resin at least one kind of thermoplastic resin selected from the group consisting of acrylic resin, polyethylene, polystyrene, polypropylene, polyvinyl chloride, polyimide, polyamide and polybenzoimidazole is preferable.
  • metal particles other than those described above, conductive particles, various additives, and the like may be coexistent, as long as the purpose of the present invention is not violated.
  • the additives include curing initiators such as energy ray curing and heat curing, curing accelerators, sensitizers, thickeners, and strength reinforcing agents.
  • the conductive composition for electrical connection of an electronic device has a great effect when used for via holes, through holes, wiring, and the like, which are electrical connection sites of an electronic device such as a circuit board.
  • (1) Filling through holes in printed wiring boards Filling, hardening, and surface polishing of the parts that connect circuits between each layer by performing hardening and surface polishing, and (2) non-through holes made by laser vias and photo vias on printed wiring boards (3) A part to connect the circuit by filling, hardening and polishing the through hole for connecting the back surface of the semiconductor, (3) A non-penetration for heat dissipation of the semiconductor (5) Printed and cured metal-containing composition on semiconductor package printed wiring board, and bump-shaped electrode sites called bumps, (6) Print Conductive conical projections formed by printing and curing on the circuit of the inner layer material in the interlayer connection of the wiring board, (7) Used as an alternative to the solder connection used when mounting printed wiring boards and semiconductor package components Ira (8) printed circuit board, printed circuit board,
  • These semiconductor devices can be manufactured, for example, as follows.
  • the printed circuit board on which the inner layer copper electrode portion is formed is irradiated with laser light, holes are drilled up to the copper electrode portion inside the printed circuit board, and the residual insulating resin, which is the printed circuit board material dissolved and evaporated by the laser light, is removed. Then, a print substrate having a non-through hole having a bottomed copper electrode portion is manufactured.
  • the non-through holes are filled with the metal-containing composition by screen printing. Thereafter, the metal-containing composition is cured by applying heat, and the surface of the printed circuit board is further polished to remove irregularities on the printed circuit board caused by the cured product. Plan.
  • copper plating is applied to the surface of the cured material portion exposed on the surface of the printed circuit board, electrodes are provided, and connection is made with the circuit portion.
  • the metal-containing composition may be screen-printed and heat-cured to form a conductive circuit (wiring).
  • Examples 1-31, 33, 35-41 are This is an example.
  • the numbers 1 to 23 in Examples 32 and 34 are examples, and the numbers 24 and 25 are comparative examples.
  • the Z value is a dimensionless number defined as the ratio of the centrifugal acceleration to the gravitational acceleration in order to compare the magnitude of the force acting on one point in the centrifugal force field. The measurements and evaluations used in the following examples were based on the following methods.
  • the powder was added to cyclohexane, and the measurement was performed by a dynamic light scattering method using laser light using Microtrack 9340-UPA manufactured by Nikkiso Co., Ltd.
  • a transmission electron microscope For observation with a transmission electron microscope, a Hitachi transmission electron microscope H-90000 was used.
  • a scanning electron microscope a scanning electron microscope S-800 manufactured by Hitachi, Ltd. was used.
  • This cured composition belongs to the category of the conductive composition according to the present invention, but this does not mean only the conductive composition according to the present invention prepared under the above conditions. As long as the requirements of the present invention described in the above embodiment are satisfied, any other cured composition belonging to the present invention belongs to the scope of the present invention.
  • Ag ultrafine particle powder as metal particle powder A was prepared as follows. In a glass container, add 1904 g of iron (II) sulfate heptahydrate and 900 ml of trinatric citrate to 100 g of distilled water 362 g of Pemuni hydrate were dissolved. To this, 625 g of a 10% aqueous solution of silver nitrate was added and stirred. Immediately after the addition, ultrafine Ag particles were formed.
  • this solution was centrifuged at 5000 rpm (Z value 2742) for 3 minutes, the supernatant was discarded, the precipitated solid was taken out, 1000 g of distilled water was added to the solid, and the deflocculation was performed. did.
  • FIG. 14 shows the particle size distribution.
  • the observation image (500,000-fold) observed by the transmission electron microscope illustrated in FIG. 15 was also in good agreement with the average particle size.
  • Ultrafine Pd particles as metal particle powder A were prepared as follows. In a glass container, 970 g of iron (II) sulfate heptahydrate and 1800 g of trinatum citrate hydrate were dissolved in 10,000 g of distilled water. To this, 2000 g of a 1% aqueous solution of palladium (II) nitrate was added and stirred. Ten minutes after the addition, ultrafine Pd particles were formed. Thereafter, desalting and concentration treatment was performed by ultrafiltration to obtain 500 g of a 1.5% sol solution in terms of Pd solid content.
  • Au ultrafine particles as metal particle powder A were prepared as follows. In a glass container, 10.4 g of salted lauric acid and 1 g of hydroxypropyl cellulose (average molecular weight: 25,000) were dissolved in 10,000 g of distilled water. To this was added a mixture of 950 g of a 1.12% aqueous solution of potassium hydroxide and 150 g of a 36% aqueous solution of formaldehyde, followed by stirring. Immediately after the addition, ultrafine Au particles were generated.
  • the solution was heated to 40 ° C, stirred for 1 hour, and subjected to ultrafiltration for desalination and concentration to obtain 300 g of a 1.2% Au solid sol solution in terms of Au solid content. .
  • Ru ultrafine particles as metal particle powder A were prepared as follows. In a glass container, 12.5 g of ruthenium chloride trihydrate (Ru40%) was dissolved in 10,000 g of distilled water. To this, 1000 g of a 3% aqueous sodium borohydride solution was added and stirred. Immediately after the addition, ultrafine particles of Ru were formed.
  • Ru40% ruthenium chloride trihydrate
  • Ag-Pd ultrafine particles (alloy) as metal particle powder A were prepared as follows. In a glass container, 194 g of iron (II) sulfate heptahydrate and 362 g of trinatridimni hydrate were dissolved in 1000 g of distilled water. A mixed solution of 625 g of a 10% aqueous silver nitrate solution and 200 g of a 1% aqueous palladium (II) nitrate solution was added thereto, followed by stirring. Immediately after the addition, ultrafine AgPd particles were formed.
  • Ultrafine Pt particles as metal particle powder A were prepared as follows. In a glass container, 970 g of iron (II) sulfate heptahydrate and 1800 g of tri-n-trinimudium citrate were dissolved in 10,000 g of distilled water. To this, 2000 g of a 1% aqueous solution of chloroplatinic acid was added and stirred. 15 minutes after the addition, ultrafine Pt particles were formed.
  • Ultra fine particles of Re as metal particle powder A were prepared as follows. In a glass container, 10.5 g of rhenium trichloride (Re 40%) was dissolved in 10,000 g of distilled water. To this, 1000 g of a 3% aqueous sodium borohydride solution was added and stirred. Immediately after the addition, ultra fine particles of Re were generated.
  • Os ultrafine particles as metal particle powder A were prepared as follows. In a glass container, 10.5 g of osmium trichloride trihydrate (Os content: 64%) was dissolved in 10,000 g of distilled water. To this, 1000 g of a 3% aqueous sodium borohydride solution was added and stirred. Immediately after the addition, ⁇ s ultrafine particles were formed.
  • Ir ultrafine particles as metal particle powder A were prepared as follows. In a glass container Then, 10.5 g of iridium trichloride hydrate (Ir content 53%) was dissolved in 10,000 g of distilled water. To this, 1000 g of a 3% aqueous sodium borohydride solution was added and stirred. Immediately after the addition, ultra fine particles of I rr were formed.
  • Ru ultrafine particles (alloy) as metal particle powder A were prepared as follows. In a glass container, 12.5 g of ruthenium chloride trihydrate (Ru40%) and 10.4 g of salted diacid were dissolved in 10,000 g of distilled water. To this, 2000 g of a 3% sodium borohydride aqueous solution was added and stirred. Immediately after the addition, Au_Ru ultrafine particles were generated.
  • Au-Pd ultrafine particles (alloy) as metal particle powder A were prepared as follows. In a glass container, 10.4 g of chloroauric acid was dissolved in 10,000 g of distilled water. To this, 2000 g of a 1% aqueous solution of palladium (II) nitrate was added and stirred. Furthermore, 2000 g of a 3% aqueous sodium borohydride solution was added to this mixed solution, and the mixture was stirred. did. Immediately after the addition, AuPd ultrafine particles were formed.
  • Au-Ag ultrafine particles (alloy) as metal particle powder A were prepared as follows. In a glass container, 10.5 g of gold hydroxide was dissolved in 1000 g of an alkaline solution whose pH was adjusted to 13 with potassium. To this was added 200 g of a 5% aqueous solution of silver nitrate and stirred. Further, 30 g of trisodium citrate dihydrate was added to the mixed solution, followed by stirring. The solution was heated to 95 ° C and stirred, and Au-Ag ultrafine particles were formed.
  • Ultrafine In particles as metal particle powder A were prepared as follows. In a glass container, 12.5 g of ruthenium trichloride trihydrate was dissolved in 10,000 g of distilled water. This solution was heated to 90 ° C., and 2,000 g of a 3% aqueous sodium borohydride solution was added with stirring. Immediately after the addition, ultrafine In particles were formed.
  • Ag particles as metal particle powder B were prepared as follows. 80 g of alcohol and 5 g of acetylacetone were added to 10 g of Ag powder having a specific surface area of 0.6 m 2 / g, and pulverized by a sand mill for 200 minutes to obtain 90 g of an Ag suspension. The obtained suspension was centrifuged at 1000 rpm (Z value 110) for 3 minutes to precipitate coarse particles, and the supernatant suspension was separated. 800 g of a 3% strength solution of stearyl acid in ethanol was added to the supernatant suspension, and the mixture was stirred. The mixture was centrifuged at 5000 rpm (Z value 2742) for 3 minutes, and the supernatant was discarded. The precipitated solid was removed. This solid was dried under reduced pressure at room temperature to obtain a powder of Ag particles. The average particle size of this powder was 900 nm. Observed images observed with a scanning electron microscope were also in good agreement with this average particle size.
  • Ru particles as metal particle powder B were prepared as follows. 80 g of alcohol and 5 g of acetylacetylacetone were added to 8 g of Ru powder having a specific surface area of 0.1 m 2 Zg, and pulverized by a sand mill for 500 minutes to obtain 90 g of a Ru suspension. The obtained suspension was centrifuged at 1000 rpm (Z value: 110) for 3 minutes to precipitate coarse particles, and the supernatant suspension was separated. 500 g of a 3% ethanol solution of stearic acid was added to the supernatant suspension, and the mixture was stirred. The mixture was centrifuged at 5000 rpm (Z value 2742) for 3 minutes, and the supernatant was discarded. The solid was removed. The solid was dried under reduced pressure at room temperature to obtain a Ru powder. The average particle size of this powder was 1,000 nm. [Example 16]
  • Ni particles as metal particle powder B were prepared as follows. 80 g of alcohol and 5 g of acetylacetone are added to 8 g of Ni powder having a specific surface area of 0.1 An ⁇ Zg generated by decomposition of carbonynickel, and pulverized by a sand mill for 500 minutes. 90 g were obtained. The obtained suspension was centrifuged at 1000 rpm (Z value: 110) for 3 minutes to precipitate coarse particles, and the supernatant suspension was separated. 800 g of a 3% strength solution of stearic acid in ethanol was added to the supernatant suspension, and the mixture was stirred. The mixture was centrifuged at 5000 rpm (Z value 2742) for 3 minutes, and the supernatant was discarded. The solid was removed. The solid was dried under reduced pressure at room temperature to obtain a Ni powder. The average particle size of this powder was 1500 nm.
  • Sn particles as metal particle powder B were prepared as follows. 80 g of alcohol and 5 g of acetyl acetone were added to 8 g of Sn powder having a specific surface area of 0.3 m 2 / g produced by the atomization method, and pulverized by a sand mill for 500 minutes to obtain a Sn suspension. 90 g were obtained. The obtained suspension was subjected to centrifugation at 1000 rpm (Z value 110) for 3 minutes to precipitate coarse particles, and the supernatant suspension was separated.
  • A1 particles as metal particle powder B were prepared as follows. 80 g of alcohol and 5 g of acetyl acetone were added to 8 g of A1 powder having a specific surface area of 0.1 lm 2 / g produced by the atomizing method, and pulverized by a sand mill for 500 minutes. 90 g were obtained. Centrifuge the obtained suspension at l OOO r pm (Z value 110) for 3 minutes Separation treatment was performed to settle coarse particles, and the supernatant suspension was separated.
  • Zn particles as metal particle powder B were prepared as follows. 80 g of alcohol and 5 g of acetyl aceton were added to 8 g of Zn powder having a specific surface area of 0.1 lm 2 Zg produced by the atomization method, and pulverized by a sand mill for 500 minutes to obtain a Zn suspension of 90 g. Got. The obtained suspension was subjected to centrifugal separation at l OOO rpm (Z value 110) for 3 minutes to precipitate coarse particles, and the supernatant suspension was separated.
  • W particles as metal particle powder B were prepared as follows. 80 g of alcohol and 5 g of acetylaceton are added to 8 g of W powder having a specific surface area of 0.1 lm 2 Zg produced by the electrolytic reduction precipitation method, and pulverized by a sand mill for 500 minutes to obtain a W suspension of 90 g. Got. The obtained suspension was centrifuged at 1000 rpm (Z value: 110) for 3 minutes to precipitate coarse particles, and the supernatant suspension was separated.
  • In particles as metal particle powder B were prepared as follows. 80 g of alcohol and 5 g of acetylacetone are added to 8 g of In powder having a specific surface area of 0.1 lm 2 / g produced by the electrolytic deposition method, and pulverized by a sand mill for 500 minutes. 90 g of a suspension was obtained. The obtained suspension was centrifuged at 1000 rpm (Z value 110) for 3 minutes to precipitate coarse particles, and the supernatant suspension was separated.
  • Cu particles as metal particle powder B were prepared as follows. 80 g of alcohol and 5 g of acetylacetone are added to 8 g of Cu powder having a specific surface area of 0.2 m 2 Zg generated by the electrolytic deposition method, and pulverized by a sand mill for 500 minutes. 0 g was obtained. The resulting suspension was subjected to centrifugation at l OOO rpm (Z value 110) for 3 minutes to precipitate coarse particles, and the supernatant suspension was separated.
  • Co particles as metal particle powder B were prepared as follows. 80 g of alcohol and 5 g of acetylaceton are added to 8 g of Co powder having a specific surface area of 0.2 m 2 / g produced by the reductive precipitation method, and pulverized by a sand mill for 500 minutes to obtain a Co suspension. 90 g were obtained. The resulting suspension was subjected to centrifugation at l OOO rpm (Z value 110) for 3 minutes to precipitate coarse particles, and the supernatant suspension was separated.
  • Ag particles as conductive particle powder C were prepared as follows. 80 g of alcohol and 5 g of acetylacetone were added to 10 g of Ag powder having a specific surface area of 0.02 m 2 Zg, and pulverized by a sand mill for 30 minutes to obtain 90 g of an Ag suspension. The obtained suspension was centrifuged at 5000 rpm (Z value: 2742) for 3 minutes to sediment the particles. This precipitate was added to 800 g of a 3% ethanol solution of stearic acid, subjected to ultrasonic dispersion for 100 minutes, and then centrifuged at 5000 rpm (Z value 274 2) for 3 minutes to remove the supernatant. It was discarded and the precipitated solid was removed. The solid was dried under reduced pressure at room temperature to obtain an Ag powder of conductive particles. The average particle size of this powder was 5 m. Observed images observed with a scanning electron microscope were also in good agreement with this average particle size.
  • Ru particles as conductive particle powder C were prepared as follows. Alcohol 80 g, the ⁇ cetyl acetone 5 g was added to 1 11 flour 10 g of a specific surface area of 0.03111 2 7, for 30 minutes peptization treatment in a sand mill to obtain a 11 suspension 90. The resulting suspension was centrifuged at 5 OOO rpm (Z value 2742) for 3 minutes to sediment the particles. This precipitate is added to 800 g of a 3% ethanol solution of stearic acid, dispersed by ultrasonic waves for 100 minutes, and then centrifuged at 5000 rpm (Z value 2742) for 3 minutes. Was discarded and the precipitated solid was removed. This solid was dried under reduced pressure at room temperature to obtain Ru powder of conductive particles. The average particle size of this powder was 16 m.
  • Cu particles as conductive particle powder C were prepared as follows. 80 g of alcohol and 5 g of acetylacetone are added to 10 g of Cu powder produced by the electrolytic deposition method with a specific surface area of 0.04 m 2 Zg, deflocculated in a sand mill for 30 minutes, and 90 g of the Cu suspension Got. The resulting suspension was centrifuged at 5000 rpm (Z value 2742) for 3 minutes to sediment the particles. This precipitate is added to 800 g of a 3% ethanol solution of stearic acid, dispersed by ultrasonic waves for 100 minutes, and then centrifuged at 5000 rpm (Z value 2742) for 3 minutes. The night was discarded and the precipitated solid was removed. The solid was dried under reduced pressure at room temperature to obtain Cu powder of conductive particles. The average particle size of this powder was 20 m.
  • ITO (tin solid solution type indium oxide) particles as conductive particle powder C were prepared as follows.
  • Shii-Dani Tin (IV) anhydrous
  • 40 g of indium trichloride anhydrous
  • the mixture was added dropwise to a 1.12% aqueous potassium hydroxide solution kept at 40 ° C. to obtain a hydroxide.
  • the solution containing the hydroxide was further heated to 90 ° C. and stirred for 6 hours. By this heating treatment, the hydroxide in the solution formed an aggregated structure.
  • Impurity ions were removed by desalting from the obtained indium monotin hydroxide having an aggregated structure, followed by baking at 800 ° C. for 2 hours in a nitrogen atmosphere to obtain a tin-containing indium oxide powder. After adding 10 g of the obtained tin-containing indium oxide powder to 50 g of an aqueous nitric acid solution adjusted to pH 5.5, the mixture was pulverized with a sand mill for 5 minutes to obtain a tin-containing zinc oxide of 12% in terms of solid content. 40 g of an indium oxide-containing suspension was obtained.
  • the obtained suspension was centrifuged at 5000 rpm (Z value 2742) for 3 minutes to sediment the particles.
  • This precipitate is added to 800 g of a 3% ethanol solution of stearic acid, and the mixture is ultrasonically dispersed for 100 minutes. (Z value: 2742), centrifuged for 3 minutes, the supernatant was discarded, and the precipitated solid was taken out.
  • the solid was dried under reduced pressure at room temperature to obtain ITO powder of conductive particles. The average particle size of this powder was 2 im.
  • ATO (antimony solid solution type tin oxide) particles which are conductive particle powder C, were prepared as follows. In a glass container, 5 g of potassium antimonyl tartrate was added to 1000 g of distilled water to prepare a solution. In addition, tin chloride (IV) (anhydrous) 40 g was added to another 1000 g of distilled water to prepare a solution. After mixing the two kinds of dissolving solutions, the mixture was added dropwise to a 1.5% aqueous solution of hydroxylated water kept at 40 ° C. to obtain tin-antimony hydroxide. The solution containing the hydroxide was further heated to 90 ° C. and stirred for 6 hours. By this heating treatment, the hydroxide in the solution formed an aggregated structure.
  • Impurity ions were removed from the obtained hydroxide having an aggregated structure by desalting, and then calcined at 550 ° C. for 2 hours under an air atmosphere to obtain antimony-containing tin oxide powder.
  • the obtained suspension was centrifuged at 5000 rpm (Z value 2742) for 3 minutes to precipitate coarse particles.
  • This precipitate was added to 800 g of a 3% ethanol solution of stearic acid in ethanol, and subjected to a dispersion treatment with ultrasonic waves for 100 minutes, followed by centrifugation at 5000 rpm (Z value 2742) for 3 minutes, and the supernatant was removed.
  • the liquid was discarded, and the precipitated solid was removed.
  • the solid was dried under reduced pressure at room temperature to obtain ATO powder of conductive particles. The average particle size of this powder was 3 nm.
  • the Ru0 2 (ruthenium oxide) particles are conductive particles powder C was prepared as follows. In a glass container, add ruthenium chloride trihydrate (Ru40 %) was added to obtain a solution. A solution of ruthenium chloride was added dropwise to a 1.5% aqueous sodium hydroxide solution kept at 40 ° C to obtain a hydroxide. The solution containing the hydroxide was further heated to 90 ° C. and stirred for 6 hours. By this heating treatment, the hydroxide in the solution formed an aggregated structure.
  • Impurity ions were removed by desalting from the resulting ruthenium hydroxide having formed an aggregated structure, and then calcined at 800 ° C for 2 hours in the atmosphere to obtain ruthenium oxide powder.
  • the mixture was peptized with a sand mill for 5 minutes, and 40 g of a 3% ruthenium oxide suspension in terms of ruthenium oxide solids was added.
  • the obtained suspension was centrifuged at 5000 rpm (Z value: 2742) for 3 minutes to precipitate coarse particles.
  • This precipitate is added to 800 g of a 3% ethanol solution of stearic acid, dispersed by ultrasonication for 100 minutes, centrifuged at 5000 rpm (Z value 2742) for 3 minutes, and the supernatant is removed. Was discarded and the precipitated solid was removed. The solid was dried under reduced pressure at room temperature to obtain Ru ⁇ 2 (ruthenium oxide) powder of conductive particles. The average particle size of this powder was 10 m.
  • a carbon nanotube as the conductive particle powder C was prepared as follows. 10 g of carbon nanotube powder of carbon nanotubes (tube length 0.5 m to 25 m, diameter 0.3 to 2 nm) obtained by the arc discharge method is a 3% concentration of stearic acid in ethanol 800 g, ultrasonically dispersed for 100 minutes, centrifuged at 5000 rpm (Z value 2742) for 3 minutes, the supernatant was discarded, and the precipitated solid was removed. The solid was dried under reduced pressure at room temperature to obtain carbon nanotube powder of conductive particles. The average particle size of this powder was 19 m.
  • the conductive carbon having a graphite structure which is a conductive particle powder C, is as follows. It was prepared as follows. 100 g of conductive carbon (trade name: Ketjen Black) having a partially graphite structure in the particles is added to 800 g of a 3% -concentration ethanol solution of stearic acid, and ultrasonically added to 100 g. After the minute dispersion treatment, the mixture was centrifuged at 500 rpm (Z value: 2742) for 3 minutes, the supernatant was discarded, and the precipitated solid was taken out. The solid was dried under reduced pressure at room temperature to obtain a conductive carbon powder partially having a graphite structure. The average particle size of this powder was 3 m.
  • metal particle powder A, metal particle powder B, resin, and in some cases, conductive particle powder C were mixed at a composition ratio shown in Table 1, and roughly kneaded in an automatic mortar for 1 hour. Then, kneading with three rolls was carried out for 60 minutes, and defoaming treatment was further performed for 1 hour with a centrifugal defoaming apparatus to prepare a metal-containing composition for electrical connection of an electronic device.
  • Nos. 1 to 23 had a viscosity in the range of about 800 dPa ⁇ s and were excellent in fluidity.
  • the examples of numbers 1 to 23 show the concentration of metal particles with a particle size of 20 nm or less and the concentration of metal particles with a particle size of 50 nm or more and 200 nm or less. And the concentration of the conductive particles having a particle diameter of more than 2000 nm and not more than 20 m satisfied the requirement of the above-described embodiment 3.
  • a particle size region of 20 nm or less and a particle size of 50 nm or more A peak was present in each of the particle size regions of less than nm and, in some cases, a peak was also present in a particle size region of more than 2000 nm and less than 20 m.
  • each pair of two holes provided on a 5.0 mm thick glass epoxy board is connected by a 15 zm thick copper electrode 101.
  • a via-hole 102 having a pore size of 50 urn and a depth of 60 / im was filled with a paste of a metal-containing composition having the composition shown in Table 1 by a screen printing method, and processed according to the conditions of the above-mentioned "Preparation of a cured composition".
  • a substrate to which the curing (crosslinking) composition was applied was obtained.
  • the resistance value (initial resistance value) of the cured composition filled in the holes was measured by measuring the resistance value between the ends of the 3000 holes.
  • the daisy chain circuit board has one cycle of -65 ° C for 30 minutes and 125 ° C for 30 minutes. After 1000 cycles of the test, the resistance value between the ends of the 3000 holes was measured. (I) Switching between 65 ° C for 30 minutes and 125 ° C for 30 minutes is performed automatically, and the time required for one switch is about 3 seconds Z times. Table 2 shows the rate of change of the resistance value. It can be understood that all of the examples are more excellent in conductivity and durability than the comparative examples. The resistance of the cured composition was specifically determined as follows.
  • the resistance value of the cured composition filled in one pier hole is calculated by dividing the resistance value between the ends of the 3,000 holes by the number of holes filled with the paste (3000).
  • FIG. Needle-like, tree-like, burrow-like and irregularly connected shapes as shown in 1 to 13 were observed.
  • Figures 17-20, 29, and 30 are cross-sectional photographs taken using a Hitachi S-800 scanning electron microscope. Figure 17 was taken at 1000x, Figure 18 was taken at 10,000x, Figure 19 was taken at 5000x, and Figures 20, 29 and 30 were taken at 10000x.
  • FIG. 21 is a model diagram showing an example of the above (1), (2), and (8).
  • the conductive composition for electrical connection of an electronic device according to the present invention is a conductor circuit portion formed on the insulating substrate 16 by printing and curing the conductor circuit. Used as wiring pattern 11, wiring pattern 14 provided inside, conductive filler in through hole covered with chemical plating layer 15, and conductive filler 13 in non-through hole covered with chemical plating layer 15. Have been.
  • FIG. 22 is a model diagram showing an example of the above (3) and (4).
  • the conductive composition for electrical connection of an electronic device according to the present invention includes a through hole 23 for back surface connection, a non-through hole 24 for heat radiation, which penetrates the silicon wafer 21 and the passivation film 22. Used in
  • FIG. 23 is a model diagram showing an example of the above (5).
  • the conductive composition for electrical connection of an electronic device according to the present invention is used as a bump 32 when a semiconductor package 31 is mounted on a print substrate 34.
  • Number 33 represents a sealing material.
  • FIG. 24 is a model diagram showing an example of the above (6).
  • the conductive composition for electrical connection of an electronic device according to the present invention includes a wiring pattern 11 provided on an insulating substrate 16 and a wiring pattern 14 provided inside.
  • the conductive conical projections 41 provided between the wiring patterns 11 and 14 are used.
  • FIG. 25 is a model diagram showing an example of the above (7).
  • the conductive composition for electrical connection of an electronic device according to the present invention includes a solder connection portion 5 2 on a gold bump 5 1 when the semiconductor package 3 1 is mounted on a print substrate 3 4. It is used as a substitute material for soldering.
  • FIG. 26 is a model diagram showing an example of the above (9).
  • the conductive composition for electrical connection of an electronic device according to the present invention is composed of a wiring pattern 11 on a printed circuit board 34 and a capacitor, which is an embedded passive element in the printed circuit board 34. It is used as an electrical connection material 63 filled in a non-through hole connecting the electrode 61 with the electrode 62.
  • composition Constituent properties No. 21 No. 22 No. 23 No. 24 No. 25 Metal particle powder A In metal-containing composition 5 4 5 0 1 Average 3 ⁇ 4 ⁇ (nm) 10 12 12 10 Cumulative number of pieces 90% 14 16 16 15:00 ⁇ 1 (nm)
  • Resin Resin type Phenolic silicone e Liimide Epoxy epoxy Cured resin Cured resin and epoxy resin Resin Resin Resin Kishi tree
  • a conductive composition for electrical connection of electronic devices which is excellent in conductivity and durability, and excellent in applicability, printability, and filling property, and a conductive composition electrical connection site
  • a highly reliable electronic device that is applied to a semiconductor device can be obtained.

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Abstract

Cette invention se rapporte à une composition conductrice pour la connexion électrique d'un dispositif électronique, ayant d'excellentes propriétés de conduction et de durabilité, ainsi que d'excellentes propriétés d'applicabilité, d'imprimabilité et de positionnement, et à un dispositif électronique de haute fiabilité, dans lequel une telle composition conductrice est appliquée sur une partie de connexion électrique. Cette composition est préparée au moyen d'un procédé, dans lequel une énergie est appliquée à une composition à teneur en métal, contenant une poudre métallique ayant une taille moyenne de particules inférieure ou égale à 20 nm, une poudre de métal ayant une taille moyenne de particules comprise entre 50 et 2 000 nm, une résine et, le cas échéant, une poudre conductrice ayant une taille moyenne de particules comprise entre 2 000 nm et 20 νm. On peut ainsi produire comme nouveauté au moins une forme choisie dans le groupe comprenant une suspension épaisse aciculaire, dendritique, et des formes connectées en mode amorphe constituées de métal ou de métal et de particules conductrices, cette forme ou ces formes ayant au moins une section transversale sélectionnée de façon arbitraire égale à 0,1 mm2.
PCT/JP2003/012011 2002-09-19 2003-09-19 Composition conductrice pour la connexion electrique d'un dispositif electronique et dispositif electronique Ceased WO2004027787A1 (fr)

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