WO2010018781A1 - 複合ナノ粒子及びその製造方法 - Google Patents
複合ナノ粒子及びその製造方法 Download PDFInfo
- Publication number
- WO2010018781A1 WO2010018781A1 PCT/JP2009/063961 JP2009063961W WO2010018781A1 WO 2010018781 A1 WO2010018781 A1 WO 2010018781A1 JP 2009063961 W JP2009063961 W JP 2009063961W WO 2010018781 A1 WO2010018781 A1 WO 2010018781A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- silver
- copper
- organic
- compound
- composite
- Prior art date
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/30—Making metallic powder or suspensions thereof using chemical processes with decomposition of metal compounds, e.g. by pyrolysis
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/0425—Copper-based alloys
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/0466—Alloys based on noble metals
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S977/00—Nanotechnology
- Y10S977/70—Nanostructure
- Y10S977/773—Nanoparticle, i.e. structure having three dimensions of 100 nm or less
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S977/00—Nanotechnology
- Y10S977/84—Manufacture, treatment, or detection of nanostructure
- Y10S977/895—Manufacture, treatment, or detection of nanostructure having step or means utilizing chemical property
- Y10S977/896—Chemical synthesis, e.g. chemical bonding or breaking
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
- Y10T428/2991—Coated
Definitions
- the present invention relates to composite nanoparticles and a method for producing the same.
- Metal nanoparticles are ultrafine particles with a particle diameter of 1 to 100 nm, and atoms existing on the surface are extremely unstable, and are known to spontaneously cause fusion and coarsening between particles. Yes. Therefore, metal nanoparticles are usually stabilized by covering the surface with an organic protecting group. Unlike bulk metals, metal nanoparticles exhibit unique physical properties such as low melting point and low temperature sintering properties, and are used as conductive pastes for wiring formation as engineering applications.
- Metal nanoparticles are often classified by synthetic methods.
- the synthesis method of metal nanoparticles is a physical method of pulverizing bulk metal to obtain particles, and generating zero-valent metal atoms from precursors such as metal salts and metal complexes, and aggregating them to obtain nanoparticles
- the pulverization method which is one of the physical methods, is a method of obtaining metal nanoparticles by grinding a metal using an apparatus such as a ball mill.
- particles obtained by this method have a wide particle size distribution, and it is difficult to obtain particles having a size of several hundred nm or less.
- Patent Document 1 Patent Document 2, etc.
- the greatest feature of this thermal decomposition control method is the simplicity of heating without solvent, and therefore, mass synthesis is possible.
- organic compound or the like having a mild reducing property to the reaction system, the reaction conditions become mild, and the particle diameter and shape, the design of the surface protective layer, and the like can be made.
- metal nanoparticles Industrial application of metal nanoparticles has been actively studied in various fields, one of which is a fine wiring technique using metal nanoparticles. Since metal nanoparticles are covered with an organic protective layer, the solvent dispersibility is high, and it is expected that wiring at low temperatures will be possible by using the low-temperature fusion phenomenon peculiar to nanoparticles. .
- Patent Document 1 a method of heat-treating a starting material containing a metal salt in the presence of an amine compound in an inert gas atmosphere has been proposed. Also, there is provided a method for producing composite metal ultrafine particles in which a starting material containing a metal salt is heat-treated in an inert atmosphere, wherein the starting material comprises (1) two or more metals and (2) at least one of N and O. A manufacturing method including the same has also been proposed (Patent Document 2). According to these production methods, metal nanoparticles having excellent dispersion stability can be provided.
- the main object of the present invention is to provide metal nanoparticles with even better migration resistance.
- the present invention relates to the following composite nanoparticles and a method for producing the same.
- General formula R 1 R 2 R 3 N (where R 1 to R 3 are the same or different from each other and each represents an optionally substituted alkyl group or aryl group, and R 1 to R 3 are cyclic
- the number of carbon atoms of R 1 to R 3 may be the same or different from each other, and is 1 to 18.)
- a tertiary amine compound represented by A method for producing composite nanoparticles characterized in that composite nanoparticles containing at least silver and copper in one particle are obtained by heat-treating a mixture containing a copper compound at 150 ° C. or higher. 2.
- the molar ratio A ′ of the silver component to the total of the silver component and the copper component in the composite nanoparticle is 0.8 A ⁇ A ′ ⁇ 1 with respect to the charged molar ratio A of the organic silver compound to the total of the organic silver compound and the organic copper compound.
- Item 2. The manufacturing method according to Item 1, which is 2A. 3.
- Item 2. The production method according to Item 1, wherein a 1,2-alkanediol having 5 or more carbon atoms and / or a derivative thereof is further present. 4). The manufacturing method of said claim
- Item 8. The composite nanoparticle according to Item 7, wherein the molar ratio of the silver component to the total of the silver component and the copper component in the composite nanoparticle is 1% or more and 99% or less. 9.
- the composite nanoparticle according to Item 7 which is used for migration-resistant bonding.
- Item 8. A paste containing the composite nanoparticles according to Item 7 and at least one of a solvent and a viscosity adjusting resin.
- 12 The step of forming an electrical junction region or pattern using the composite nanoparticle according to Item 7 or a paste containing the particle, and firing the electrical junction region or pattern in a reducing atmosphere at 400 ° C. or lower.
- a method for forming an electrical junction or an electrical circuit comprising a step of obtaining an electrical junction or an electrical circuit comprising a fired body.
- Item 13 The method according to Item 12, wherein the internal structure of the fired body has a structure in which the composite nanoparticles are fused to each other. 14 Item 15.
- 15. 13 An electrical junction or an electrical circuit obtained by the method according to item 12, wherein the internal structure of the fired body has a structure in which composite nanoparticles are fused to each other. . 16.
- Item 16 The electrical junction or circuit according to Item 15, wherein the structure is a three-dimensional network structure.
- composite nanoparticles containing silver and copper in one particle can be suitably produced.
- the nanoparticles obtained by the prior art are a mixture of silver particles and copper particles.
- the production method of the present invention it is possible to efficiently produce composite nanoparticles without precipitation of particles consisting of one component alone.
- composite nanoparticles having a ratio that is the same as or close to the ratio of raw material silver / copper can be obtained.
- 1,2-alkanediol is present in the starting material, composite nanoparticles having a composition close to the charged ratio can be obtained more reliably.
- the composite nanoparticle of the present invention is unique in that one particle contains at least silver and copper, and particles having a composition containing more silver than copper and particles containing a composition containing more copper than silver are mixed. Therefore, migration resistance superior to conventional metal nanoparticles (composite nanoparticles) can be exhibited.
- composite nanoparticles containing gold and silver, composite nanoparticles containing silver and palladium, etc. are known, but it is necessary to improve in terms of migration resistance, etc. This improvement in migration resistance Can be realized by the composite nanoparticles of the present invention.
- the composite nanoparticles of the present invention having such characteristics exhibit various properties (catalytic activity, conductivity, ultraviolet shielding property, heat ray shielding property, antibacterial property, antifouling property, rust prevention property, anticorrosion property, etc.). be able to. For this reason, for example, electronic materials (printed wiring, conductive materials, optical elements, etc.), catalyst materials (fast reaction catalysts, sensors, etc.), structural materials (far infrared materials, composite film forming materials, etc.), ceramics / metal materials ( Sintering aids, coating materials, etc.) and medical materials can be used widely.
- the composite nanoparticles of the present invention can be suitably used for wiring formation requiring migration resistance or joining for high temperature solder replacement.
- thermogravimetric (TG) change by the TG / DTA measurement of the powder obtained in Example 1 is shown.
- the result of the X-ray diffraction analysis (XRD) of the powder obtained in Example 1 is shown.
- the TEM image and particle size distribution of the powder obtained in Example 1 are shown.
- the result of the thermogravimetric (TG) change by the TG / DTA measurement of the powder obtained in Example 4 is shown.
- the result of the X-ray diffraction analysis (XRD) of the powder obtained in Example 4 is shown.
- the TEM image and particle size distribution of the powder obtained in Example 4 are shown.
- the result of the thermogravimetric (TG) change by the TG / DTA measurement of the powder obtained in Example 5 is shown.
- the result of the X-ray diffraction analysis (XRD) of the powder obtained in Example 5 is shown.
- the TEM image and particle size distribution of the powder obtained in Example 5 are shown.
- the result of the thermogravimetric (TG) change by the TG / DTA measurement of the powder obtained in Example 6 is shown.
- the result of the X-ray diffraction analysis (XRD) of the powder obtained in Example 6 is shown.
- the TEM image and particle size distribution of the powder obtained in Example 6 are shown.
- the result of the thermogravimetric (TG) change by the TG / DTA measurement of the powder obtained in Example 7 is shown.
- the result of the X-ray diffraction analysis (XRD) of the powder obtained in Example 7 is shown.
- Example 7 The TEM image and particle size distribution of the powder obtained in Example 7 are shown.
- the result of the thermogravimetric (TG) change by the TG / DTA measurement of the powder obtained in Example 8 is shown.
- the result of the X-ray diffraction analysis (XRD) of the powder obtained in Example 8 is shown.
- the TEM image and particle size distribution of the powder obtained in Example 8 are shown.
- the result of the thermogravimetric (TG) change by the TG / DTA measurement of the powder obtained in Example 9 is shown.
- the result of the X-ray diffraction analysis (XRD) of the powder obtained in Example 9 is shown.
- the TEM image and particle size distribution of the powder obtained in Example 9 are shown.
- the result of the X-ray diffraction analysis (XRD) of the powder obtained in Example 10 is shown.
- the TEM image and particle size distribution of the powder obtained in Example 10 are shown.
- the result of the thermogravimetric (TG) change by the TG / DTA measurement of the powder obtained in Example 11 is shown.
- the result of the X-ray diffraction analysis (XRD) of the powder obtained in Example 11 is shown.
- the TEM image and particle size distribution of the powder obtained in Example 11 are shown.
- the result of the thermogravimetric (TG) change by the TG / DTA measurement of the powder obtained in Example 12 is shown.
- the result of the X-ray diffraction analysis (XRD) of the powder obtained in Example 12 is shown.
- the TEM image of the powder obtained in Example 12 is shown.
- the result of the thermogravimetric (TG) change by the TG / DTA measurement of the powder obtained in Example 13 is shown.
- the result of the X-ray diffraction analysis (XRD) of the powder obtained in Example 13 is shown.
- the TEM image of the powder obtained in Example 13 is shown.
- the result of the thermogravimetric (TG) change by the TG / DTA measurement of the powder obtained in Example 14 is shown.
- the result of the X-ray diffraction analysis (XRD) of the powder obtained in Example 14 is shown.
- the TEM image of the powder obtained in Example 14 is shown.
- the result of the thermogravimetric (TG) change by the TG / DTA measurement of the powder obtained in Example 15 is shown.
- Example 15 The result of the X-ray diffraction analysis (XRD) of the powder obtained in Example 15 is shown.
- the TEM image of the powder obtained in Example 15 is shown.
- the result of the X-ray diffraction analysis (XRD) of the powder obtained in Example 16 is shown.
- the TEM image of the powder obtained in Example 16 is shown.
- Test Example 1 an SEM photograph of the surface of the film obtained by firing at 350 ° C. for 30 minutes in the air is shown.
- Experiment 1 the SEM photograph of the cross section of the film
- Test Example 1 an SEM photograph of a cross-section of a film obtained by firing at 350 ° C. for 30 minutes in the air and then firing at 350 ° C. for 30 minutes in a reducing atmosphere is shown.
- the method for producing composite nanoparticles of the present invention has the general formula R 1 R 2 R 3 N (provided that R 1 to R 3 may be the same or different from each other and have a substituent). A good alkyl group or an aryl group, and R 1 to R 3 may be linked in a cyclic manner. The carbon numbers of R 1 to R 3 are the same or different and are 1 to 18). It is possible to obtain composite nanoparticles containing at least silver and copper in one particle by heat-treating a mixture containing an organic silver compound and an organic copper compound in a non-oxidizing atmosphere in the presence of an amine compound at 150 ° C. or higher. Features.
- the organic silver compound in the present invention includes silver carbonate of organic acid, silver carbonate, silver alkoxide, silver acetylacetonate, and the like. These 1 type (s) or 2 or more types can be used.
- a silver salt of an organic acid can be suitably used as the organic silver compound.
- silver salts include stearate, naphthenate, octylate, octanoate, benzoate, n-decanoate, paratoluate, butyrate, caproate, palmitate, Monocarboxylates such as oleate, myristate, laurate, linoleate, linolenate, ricinoleate, malonate, succinate, maleate, fumarate, isophthalic acid Examples thereof include dicarboxylates such as salts, terephthalate, glutarate, adipate, tartrate, citrate, and pyruvate. Among these, it is more preferable to use a silver salt of an organic acid having 5 or more carbon atoms (particularly 6 or more, more preferably 8 to 14 carbon atoms).
- the organic copper compound in the present invention includes copper alkoxide, copper acetylacetonate and the like in addition to a copper salt of an organic acid. These 1 type (s) or 2 or more types can be used.
- a copper salt of an organic acid can be suitably used as the organic copper compound.
- a copper salt include stearate, naphthenate, octylate, octanoate, benzoate, n-decanoate, paratoluate, butyrate, caproate, palmitate, Monocarboxylates such as oleate, myristate, laurate, linoleate, linolenate, ricinoleate, malonate, succinate, maleate, fumarate, isophthalic acid Examples thereof include dicarboxylates such as salts, terephthalate, glutarate, adipate, tartrate, citrate, and pyruvate. Among these, it is more preferable to use a copper salt of an organic acid having 5 or more carbon atoms (particularly 6 or more carbon atoms, more preferably 8 to 14 carbon atoms).
- R 1 R 2 R 3 N As the tertiary amine compound, a general formula R 1 R 2 R 3 N (wherein R 1 to R 3 are the same or different from each other and each represents an optionally substituted alkyl group or aryl group; 1 to R 3 may be connected in a ring, and R 1 to R 3 have the same or different carbon number of 1 to 18.
- the substituent include amino group, halogen group, nitro group, nitroso group, mercapto group, sulfo group, sulfino group, hydroxyl group, methoxy group, ethoxy group, cyano group, carboxyl group, carbonyl group, phenyl group, phenoxy group. Benzoyl group, acetyl group and the like.
- the carbon number of the alkyl group or aryl group (however, when it has a substituent, the carbon number of the substituent is included) is usually about 1 to 18 for an alkyl group, particularly 4 to 12, and usually for an aryl group. It is preferably about 6 to 18, particularly 6 to 12.
- Specific examples of preferred tertiary amine compounds include trioctylamine, tributylamine, triisobutylamine, N, N-diisopropylethylamine, tris (2-ethylhexyl) amine and the like. These can be used alone or in combination of two or more.
- the amount of the tertiary amine compound used can be appropriately set according to the type of the tertiary amine compound to be used, etc., but is usually 100 to 300 moles, particularly 150 to 300 moles relative to a total of 100 moles of the organic copper compound and the organic silver compound. It is preferable to set it as 250 mol.
- amines other than tertiary amines may be present as long as the effects of the present invention are not affected, but preferably primary amines and secondary amines.
- Heat treatment is performed under conditions where no amine is present. This makes it possible to more reliably obtain composite nanoparticles having desired migration resistance.
- 1,2-alkanediol having 5 or more carbon atoms and / or a derivative thereof (hereinafter also referred to as “the diol of the present invention”) be further present.
- the presence of the diol of the present invention makes it possible to obtain composite nanoparticles having a silver / copper composition closer to the charging ratio.
- the number of carbon atoms is preferably 6 or more, more preferably 10 or more, and most preferably 12 to 30.
- 1,2-alkanediol examples include 1,2-hexanediol, 1,2-octanediol, 1,2-nonanediol, 1,2-decanediol, 1,2-undecanediol, 1, Examples thereof include 2-dodecanediol and 1,2-tridecanediol.
- the 1,2-alkanediol is preferably a linear alkanediol.
- guide_body what substituted the hydrogen atom on carbon of ethylene glycol with the other substituent is mentioned.
- substituents in this case include amino group, halogen group, nitro group, nitroso group, mercapto group, sulfo group, sulfino group, methoxy group, ethoxy group, cyano group, carboxyl group, carbonyl group, phenyl group, phenoxy group. Benzoyl group, acetyl group and the like.
- the carbon number in the case of the said derivative is carbon number including the carbon number of a substituent.
- the amount of the diol of the present invention is not limited, but it is usually preferably 100 to 300 mol, particularly 150 to 250 mol, based on a total of 100 mol of the organic copper compound and the organic silver compound.
- the heat treatment is performed at a temperature of 150 ° C. or higher in a non-oxidizing atmosphere. Thereby, a predetermined composite nanoparticle can be obtained.
- the heat treatment atmosphere is not limited as long as it is a non-oxidizing atmosphere, and may be, for example, an inert gas or a reducing atmosphere.
- the heat treatment can be carried out more preferably in an inert gas.
- the inert gas for example, nitrogen, carbon dioxide, argon, helium or the like can be used.
- the heat treatment temperature is usually 150 ° C. or higher, preferably 160 ° C. or higher.
- the upper limit may be a temperature lower than the complete decomposition temperature of the organic copper compound or organic silver compound to be used, but is usually 250 ° C. or lower.
- the complete decomposition temperature is a temperature at which the organic component of the organic copper compound or organic silver compound is completely decomposed. In this invention, it can set suitably according to the kind etc. of an organic copper compound and an organic silver compound within this temperature range.
- the heat treatment temperature may be maintained within a temperature range of 100 to 400 ° C.
- the heat treatment can be suitably performed within a temperature range of 100 to 250 ° C. (particularly 100 to 200 ° C.).
- the holding time of the heat treatment temperature can be appropriately changed according to the heat treatment temperature, the type of organic copper compound or organic silver compound used, and the like.
- a purification method a known purification method can be applied. For example, centrifugation, membrane purification, solvent extraction and the like may be performed.
- Composite nanoparticles having a component molar ratio A ′ of 0.8A ⁇ A ′ ⁇ 1.2A (particularly 0.9A ⁇ A ′ ⁇ 1.1A) can be obtained. That is, in the production method of the present invention, composite nanoparticles (particle group) having the same composition as the preparation ratio (silver component / copper component) or close to it can be obtained. This can be controlled more reliably by at least one of 1) the heat treatment temperature, 2) the silver / copper charge ratio, and 3) the diol addition of the present invention.
- the composite nanoparticle of the present invention is a composite nanoparticle containing an organic component, wherein at least silver and copper are contained in one particle, and particles having a composition containing more silver than copper Is characterized by being mixed with particles having a composition containing more than silver.
- the composite nanoparticle of the present invention contains an organic component, silver and copper.
- the composite nanoparticle of the present invention is preferably obtained by the production method of the present invention. That is, the general formula R 1 R 2 R 3 N (wherein R 1 to R 3 are the same or different from each other and each represents an optionally substituted alkyl group or aryl group, and R 1 to R 3 are The organic silver compound may be connected in a ring.
- the organic silver compound is a non-oxidizing atmosphere in the presence of a tertiary amine compound represented by R 1 to R 3 having the same or different carbon number of 1 to 18.
- a composite nanoparticle obtained by a method for producing a composite nanoparticle wherein a composite nanoparticle containing at least silver and copper in one particle is obtained by heat-treating the mixture containing the organic copper compound at 150 ° C. or higher It is desirable that
- the organic component is not particularly limited, since the composite nanoparticle of the present invention is preferably obtained by the production method of the present invention, the organic component includes a tertiary amine compound, an organic silver compound and an organic copper used as starting materials. It is preferable that at least 1 sort (s) of a compound and these origin components is included.
- the origin component in this case is preferably an organic component generated by subjecting the tertiary amine compound, organic silver compound and organic copper compound used as starting materials to the heat treatment.
- the tertiary amine compound In the case of using 1,2-alkanediol and / or a derivative thereof, at least one of the tertiary amine compound, the organic silver compound, the organic copper compound, the 1,2-alkanediol and / or a derivative thereof, and components derived therefrom. It is preferable that 1 type is included.
- the derived component in this case is an organic component generated by subjecting the tertiary amine compound, organic silver compound, organic copper compound, and 1,2-alkanediol and / or derivative thereof used as the starting material to the heat treatment. Is preferred.
- the content of the organic component is not particularly limited, but it is usually preferably 55% by weight or less, particularly preferably 30% by weight or less. Although the lower limit of the content of the organic component is not limited, it may be usually about 0.5% by weight.
- the ratio of silver and copper in the composite nanoparticles (particle group) is not particularly limited as long as both are included in one particle.
- the molar ratio of the silver component to the total of the silver component and the copper component in the particle group is 1% or more and 99% or less, preferably 5% or more and 85% or less.
- the composite nanoparticle of the present invention includes particles having a composition containing more silver than copper (hereinafter also referred to as “silver-rich particles”) and particles having a composition containing more copper than silver (hereinafter referred to as “copper-rich particles”). Mixed). That is, silver rich particles and copper rich particles are mixed.
- silver-rich particles particles having a composition containing more silver than copper
- copper-rich particles particles having a composition containing more copper than silver
- the average particle size of the composite nanoparticles of the present invention is not particularly limited, but is usually about 3 to 300 nm, preferably 3 to 50 nm.
- the composite nanoparticles of the present invention are excellent in dispersion stability, they are in a solubilized state when dispersed in a solvent, for example. For this reason, for example, it can be suitably used as a paste containing at least one kind of solvent and viscosity adjusting resin and composite nanoparticles.
- the solvent is not particularly limited. For example, terpene solvents, ketone solvents, alcohol solvents, ester solvents, ether solvents, aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, cellosolve solvents, carbitol solvents. A solvent etc. are mentioned.
- organic solvents such as terpineol, methyl ethyl ketone, acetone, isopropanol, butyl carbitol, decane, undecane, tetradecane, benzene, toluene, hexane, diethyl ether, and kerosene can be exemplified.
- the viscosity adjusting resin is not limited.
- a thermosetting resin such as a phenol resin, a melamine resin, or an alkyd resin
- a thermoplastic resin such as a phenoxy resin or an acrylic resin
- curing agent curable resin such as an epoxy resin, or the like.
- the content of the composite nanoparticles can be appropriately set in the range of 20 to 90% by weight.
- the present invention includes 1) a step of forming an electrical junction region or pattern with the composite nanoparticles of the present invention or a paste containing the same, and 2) firing the electrical junction region or pattern in a reducing atmosphere at 400 ° C. or lower. Also included is a method of forming an electrical junction or electrical circuit comprising the step of obtaining an electrical junction or electrical circuit.
- a method similar to soldering for joining two circuits can be employed.
- the process for forming the pattern may use a method employed in known circuit formation, electrode formation, or the like.
- a predetermined circuit pattern, electrode pattern, or the like can be formed by a printing method such as screen printing or inkjet printing.
- the firing temperature can be appropriately set according to the type of composite nanoparticles used, the paste composition, etc., but is usually 400 ° C. or lower, preferably 150 to 400 ° C., more preferably 180 to 380 ° C. The temperature is preferably 280 to 380 ° C.
- an atmosphere containing a reducing gas may be used.
- a mixed gas atmosphere containing 1 to 10% by volume of hydrogen gas and the remainder being an inert gas can be suitably employed.
- the inert gas in addition to argon gas, helium gas, etc., nitrogen gas can also be used.
- the firing time can be appropriately set according to the firing temperature and the like, but is usually about 1 to 10 hours.
- the firing temperature is usually 150 to 400 ° C., preferably 280 to 380 ° C.
- the composite nanoparticles of the present invention or a paste containing the composite nanoparticles are used, and this is fired (heat treated) in a reducing atmosphere. Since a film having a deposited structure can be formed, an electrically bonded region or pattern (an electrode pattern, a circuit pattern, or a wiring pattern) having high conductivity can be provided.
- the electrical junction region or pattern is usually in the form of a film, and the film thickness is usually 1 to 50 ⁇ m, preferably 1 to 10 ⁇ m.
- Reagents and measuring instruments ⁇ Reagents used for synthesis and measurement: 1,2-dodecanediol, trioctylamine, octanoic acid, silver carbonate from Nacalai Tesque Co., Ltd., and copper octanoate from Mitsuwa Chemicals Co., Ltd. The purchased one was used without purification.
- TG / DTA measurement The measurement was performed under a nitrogen atmosphere using a “SSC / 5200” thermal analyzer manufactured by Seiko Denshi Kogyo.
- the observation sample was prepared by adding a toluene solution to the composite nanoparticles and dispersing the solution by ultrasonic irradiation onto a copper grid with a carbon support film, followed by drying.
- Energy dispersive X-ray analysis (EDX): performed using “JEM2100IM” manufactured by JEOL.
- Fluorescence X-ray analysis (XRF) Performed using “Micro Element Monitor SEA5120” manufactured by Seiko Instruments Inc.
- Average particle diameter Measured with the above-mentioned transmission electron microscope, the arithmetic average value of the diameter of 300 arbitrarily selected particles was determined, and the value was taken as the average particle diameter.
- Content of metal component It was determined by TG / DTA measurement using the thermal analyzer.
- the reaction time in Example 1 was changed from 24 hours to 4 hours.
- the reaction time in Example 1 was changed from 24 hours to 16 hours.
- the reaction temperature in Example 2 was changed from 160 ° C. to 180 ° C. Was reacted in the same manner as in Example 2 to give a blue-violet powder (yield: 0.49 g, metal content: 84%, composition ratio: silver 50 mol%, copper: 50 mol%, average particle size: 4.0 ⁇ 0.0). 71 nm).
- the result of thermogravimetric (TG) change by TG / DTA measurement of the obtained powder is shown in FIG. 4, the result of X-ray diffraction analysis (XRD) is shown in FIG. 5, and the TEM image and particle size distribution are shown in FIG. Show.
- the fatty acid silver C 13 Ag used in Example 1 was converted to C 7 Ag Except for the change, blue violet powder (yield: 0.40 g, metal content: 91%, composition ratio: silver 58 mol%, copper 42 mol%, average particle size 5. 7 ⁇ 0.79 nm).
- the result of thermogravimetric (TG) change by TG / DTA measurement of the obtained powder is shown in FIG. 7, the result of X-ray diffraction analysis (XRD) is shown in FIG. 8, and the TEM image and particle size distribution are shown in FIG. Show.
- the fatty acid silver C 13 Ag used in Example 1 was converted to C 17 Ag. Except for the change, the reaction was carried out in the same manner as in Example 1 to give a blue-violet powder (yield; 0.52 g, metal content 83%, composition ratio silver 58 mol%: copper 42 mol%, average particle size 4.1 ⁇ ) 2.3 nm).
- the result of thermogravimetric (TG) change by TG / DTA measurement of the obtained powder is shown in FIG. 10
- the result of X-ray diffraction analysis (XRD) is shown in FIG. 11
- the TEM image and particle size distribution are shown in FIG. Show.
- Example 7 C 13 Ag / (C 7) 2 Cu / (C 8) 3 N
- reagent amounts C 8) plus 3 N (2.1 g, 6.0 mmol)
- C 7 COO C 7 COO 2 Cu (0.35 g, 1.0 mmol)
- C 13 COOAg C 13 COOAg
- blue-violet powder yield 0.44 g, metal content 80%, composition ratio silver 89 mol%: copper 11 mol%, average particle size 4.2 ⁇ 0.49 nm
- thermogravimetric (TG) change by TG / DTA measurement of the obtained powder is shown in FIG. 13
- the result of X-ray diffraction analysis (XRD) is shown in FIG. 14
- the TEM image and particle size distribution are shown in FIG. Show.
- the amount of added reagent was (C 8 ) 3 Example 5 except that N (2.1 g, 6.0 mmol), (C 7 COO) 2 Cu (0.35 g, 1.0 mmol) and C 7 COOAg (1.0 g, 4.0 mmol) were used.
- N 2.1 g, 6.0 mmol
- (C 7 COO) 2 Cu (0.35 g, 1.0 mmol
- C 7 COOAg 1.0 g, 4.0 mmol
- thermogravimetric (TG) change by TG / DTA measurement of the obtained powder is shown in FIG. 16
- XRD X-ray diffraction analysis
- the amount of added reagent was (C 8 ) 3 Example 6 except that N (2.1 g, 6.0 mmol), (C 7 COO) 2 Cu (0.35 g, 1.0 mmol) and C 17 COOAg (1.6 g, 4.0 mmol) were used.
- N 2.1 g, 6.0 mmol
- (C 7 COO) 2 Cu (0.35 g, 1.0 mmol
- C 17 COOAg 1.6 g, 4.0 mmol
- thermogravimetric (TG) change by TG / DTA measurement of the obtained powder is shown in FIG. 19
- XRD X-ray diffraction analysis
- the amount of the added reagent was (C 8 ) 3 Example 6 except that N (3.2 g, 9.0 mmol), (C 7 COO) 2 Cu (1.4 g, 4.0 mmol) and C 17 COOAg (0.40 g, 1.0 mmol) were used.
- N 3.2 g, 9.0 mmol
- (C 7 COO) 2 Cu 1. g, 4.0 mmol
- C 17 COOAg 0.40 g, 1.0 mmol
- a blue-violet powder yield 0.22 g, metal content 99%, composition ratio silver 41 mol%: copper 59 mol%, average particle diameter 21 ⁇ 8.9 nm
- XRD X-ray diffraction analysis
- a blue-violet powder Yield 2.5 g, metal content 85%, silver composition 59 mol%: copper 41 mol%, average particle diameter 3.9 ⁇ 0.71 nm.
- the result of thermogravimetric (TG) change by TG / DTA measurement of the obtained powder is shown in FIG. 24, the result of X-ray diffraction analysis (XRD) is shown in FIG. 25, and the TEM image and particle size distribution are shown in FIG. Show.
- Heat treatment was carried out under the same conditions as in No. 3 to obtain a blue-violet powder (yield 0.585 g, metal content 73%, composition ratio silver 57 mol%: copper 43 mol%, average particle size 3.59 ⁇ 0.52 nm) .
- the result of the thermogravimetric (TG) change by TG / DTA measurement of the obtained powder is shown in FIG. 27, the result of X-ray diffraction analysis (XRD) is shown in FIG. 28, and the TEM image is shown in FIG.
- the amount of the added reagent was 1.21 g (6 mmol) of 1,2-DDO. ), (C 8 ) 3 N (2.12 g, 6 mmol), (C 7 COO) 2 Cu (0.35 g, 1 mmol) and C 13 COOAg (1.34 g, 4 mmol).
- the amount of the added reagent was 1.82 g (9 mmol) of 1,2-DDO. ), (C 8 ) 3 N (3.18 g, 9 mmol), (C 7 COO) 2 Cu (1.40 g, 4 mmol) and C 13 COOAg (0.335 g, 1 mmol).
- the amount of added reagent was 1.97 g (9 .75 mmol), (C 8 ) 3 N (3.45 g, 9.75 mmol), (C 7 COO) 2 Cu (1.66 g, 4.75 mmol) and C 13 COOAg (0.084 g, 0.25 mmol).
- C 17 COOAg was changed to Ag 2 CO 3 (0.138 g, 0.5 mmol)
- C 7 COOH (0.144 g, 1 mmol) was added, a blue-violet powder was obtained (yield 0.366 g, metal content 99%, composition)
- the result of X-ray diffraction analysis (XRD) of the obtained powder is shown in FIG. 39, and the TEM image is shown in FIG. Moreover, the TEM / EDX analysis (FIG. 40) of the Ag / Cu bimetallic nanoparticle obtained in Example 16 was performed. The Ag / Cu composition ratio in each of the large particle A and the small particle B was examined. The results are shown in Table 1. As is clear from the results in Table 1, it can be seen that both silver and copper are contained in one particle. It can also be seen that copper-rich particles (FIG. 40, measurement point A) and silver-rich particles (FIG. 40, measurement point B) are mixed.
- the particle diameter of the silver-rich particles A is smaller than the particle diameter of the copper-rich B particles, and the composition ratio varies depending on the particle diameter. .
- (C 7 COO) 2 Cu decomposes after Ag 2 CO 3 , which has a relatively low decomposition temperature, decomposes and begins to form a composite of silver and copper. It is considered that silver-rich particles that are stable in particle diameter and copper-rich particles that are stable in a large particle diameter are formed by sufficiently combining silver and copper.
- FIGS. 41 and 42 show SEM photographs of the surface and cross section of the fired film A, respectively.
- an electrode pattern produced by printing in the same manner was baked at 350 ° C. for 30 minutes in the air, and then baked at 350 ° C. for 30 minutes in a reducing atmosphere containing 3% by volume of hydrogen in nitrogen.
- 43 and 44 show SEM photographs of the surface and cross section of the obtained thin film B, respectively.
- FIGS. 41 and 42 it can be seen that the sintered film is formed while maintaining the shape of the particles in the firing in the atmosphere.
- FIGS. 41 and 42 it can be seen that the sintered film is formed while maintaining the shape of the particles in the firing in the atmosphere.
- Example 2 Examination of migration resistance of Ag / Cu composite nanoparticles Ion migration is a phenomenon in which the metal of the anode is ionized and eluted by flowing electricity through an electronic circuit under high humidity and high temperature, and the electrodes are short-circuited.
- the electrode was formed by adding a dispersant (0.08 g) to an agate bowl and terpineol (0.25 g) to a solvent, and dropping a few drops of toluene to promote dispersibility. Furthermore, the said nanoparticle was added, and toluene was volatilized away and it mixed until it did not remain
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Metallurgy (AREA)
- Mechanical Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Composite Materials (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
- Powder Metallurgy (AREA)
- Conductive Materials (AREA)
- Non-Insulated Conductors (AREA)
Abstract
Description
1. 一般式R1R2R3N(但し、R1~R3は、互いに同一又は異なって、置換基を有していても良いアルキル基又はアリール基を示し、R1~R3は環状につながっていても良い。R1~R3の炭素数は、互いに同一又は異なって1~18である。)で示される3級アミン化合物の存在下、非酸化性雰囲気下で有機銀化合物及び有機銅化合物を含む混合物を150℃以上で熱処理することによって、1つの粒子中に少なくとも銀と銅を含む複合ナノ粒子を得ることを特徴とする複合ナノ粒子の製造方法。
2. 有機銀化合物及び有機銅化合物の合計に対する有機銀化合物の仕込みモル比Aに対して、複合ナノ粒子における銀成分及び銅成分の合計に対する銀成分のモル比A’が0.8A≦A’≦1.2Aである、前記項1に記載の製造方法。
3. 炭素数5以上の1,2-アルカンジオール及び/又はその誘導体をさらに存在させる、前記項1に記載の製造方法。
4. 熱処理温度が250℃以下である、前記項1に記載の製造方法。
5. 仕込みモル比Aを1%以上99%以下とする、前記項1に記載の製造方法。
6. 有機銀化合物が脂肪酸銀であり、有機銅化合物が脂肪酸銅である、前記項1に記載の製造方法。
7. 有機成分を含む複合ナノ粒子であって、1つの粒子中に少なくとも銀と銅を含み、銀が銅よりも多く含まれる組成の粒子と銅が銀よりも多く含まれる組成の粒子とが混在することを特徴とする複合ナノ粒子。
8. 複合ナノ粒子における銀成分及び銅成分の合計に対する銀成分のモル比が1%以上99%以下である、前記項7に記載の複合ナノ粒子。
9. 耐マイグレーション性配線形成用である、前記項7に記載の複合ナノ粒子。
10. 耐マイグレーション性接合用である、前記項7に記載の複合ナノ粒子。
11. 前記項7に記載の複合ナノ粒子と、溶剤及び粘度調整用樹脂の少なくとも1種とを含むペースト。
12. 前記項7に記載の複合ナノ粒子又はその粒子を含むペーストを用いて電気的接合領域又はパターンを形成する工程、前記の電気的接合領域又はパターンを還元性雰囲気中400℃以下で焼成することにより焼成体からなる電気的接合又は電気回路を得る工程を含む、電気的接合又は電気回路の形成方法。
13. 焼成体の内部構造が、複合ナノ粒子どうしが互いに融着した構造を有する、前記項12に記載の方法。
14. 前記構造が三次元網目状構造である、前記項14に記載の電気的接合又は電気回路。
15. 前記項12の形成方法により得られた電気的接合又は電気回路であって、焼成体の内部構造が、複合ナノ粒子どうしが互いに融着した構造を有することを特徴とする電気的接合又は電気回路。
16. 前記構造が三次元網目状構造である、前記項15に記載の電気的接合又は電気回路。
本発明の複合ナノ粒子の製造方法は、一般式R1R2R3N(但し、R1~R3は、互いに同一又は異なって、置換基を有していても良いアルキル基又はアリール基を示し、R1~R3は環状につながっていても良い。R1~R3の炭素数は、互いに同一又は異なって1~18である。)で示される3級アミン化合物の存在下、非酸化性雰囲気下で有機銀化合物及び有機銅化合物を含む混合物を150℃以上で熱処理することによって、1つの粒子中に少なくとも銀と銅を含む複合ナノ粒子を得ることを特徴とする。
本発明の複合ナノ粒子は、有機成分を含む複合ナノ粒子であって、1つの粒子中に少なくとも銀と銅を含み、銀が銅よりも多く含まれる組成の粒子と銅が銀よりも多く含まれる組成の粒子とが混在することを特徴とする。
・合成及び測定に用いた試薬:1,2-ドデカンジオール、トリオクチルアミン、オクタン酸、炭酸銀はナカライテスク株式会社より、オクタン酸銅は三津和化学薬品株式会社より購入したものを精製することなく使用した。
・TG/DTA測定:セイコー電子工業製「SSC/5200」熱分析装置を用いて窒素雰囲気下で行った。
・粉末X線回折装置(XRD):Rigaku製「RINT2500」を用いて行った。
・透過型電子顕微鏡(TEM)観察:日本電子製「JEM2100IM」を使用した。なお、観察試料は、複合ナノ粒子にトルエンを加えて超音波照射によって分散させた液をカーボン支持膜付き銅グリッド上に滴下し、乾燥して調製した。
・エネルギー分散X線分析(EDX):日本電子製「JEM2100IM」を用いて行った。
・蛍光X線分析(XRF):セイコーインスツルメンツ株式会社製「マイクロエレメントモニターSEA5120」を用いて行った。
本実施例では、略号として、下記の表記を用いた。
・鎖長の異なる脂肪酸銀CmH2m+1COOAg:CmCOOAg(m = 7, 13, 17)
・オクタン酸銅 (C7H15COO)2Cu:(C7COO)2Cu
・トリオクチルアミン (C8H17)3N:(C8)3N
・1,2-ドデカンジオールC10H21CH(OH)CH2(OH):1,2-DDO
・オクタン酸C7H15COOH:C7COOH
・CmCOOAgと(C8)3Nから合成した銀ナノ粒子:CmAg /(C8)3N(m = 7, 13, 17)
・CmCOOAgと(C7COO)2Cuと(C8)3Nから合成したAg/Cu複合ナノ粒子:CmAg /(C7)2Cu /(C8)3N(m = 7, 13, 17)(仕込み比、反応温度×反応時間)
・C13COOAgと(C7COO)2Cuと(C8)3Nと1,2-DDOから合成したAg/Cu複合ナノ粒子:C13Ag /(C7)2Cu
/(C8)3N/1,2-DDO(仕込み比、反応温度×反応時間)
・Ag2CO3と(C7COO)2Cuと(C8)3NとC7COOHから合成したAg/Cu複合ナノ粒子:Ag2CO3 /(C7)2Cu
/(C8)3N/ C7COOH(仕込み比、反応温度×反応時間)と表記
平均粒子径:前記の透過型電子顕微鏡により測定し、任意に選んだ粒子300個の直径の算術平均値を求め、その値をもって平均粒子径とした。
金属成分の含有量:前記の熱分析装置を用い、TG/DTA測定することにより求めた。
C13Ag /(C7)2Cu /(C8)3N(銀:銅=5:5、160℃×24時間)の合成
(C8)3N(2.7g,7.5mmol)と(C7COO)2Cu(0.88g,2.5mmol)とC13COOAg(0.84g,2.5mmol)を160℃で24時間保持した後、室温まで冷却した。冷却後、アセトン(10ml)とメタノール(10ml)の混合液で洗浄し、桐山ロートで濾過後、減圧下で乾燥し青紫色粉末(収量0.45g,金属含有率86%,組成比 銀54mol%:銅46mol%,平均粒子径4.1±0.87nm)を得た。得られた粉末のTG/DTA測定による熱重量(TG)変化の結果を図1に示し、X線回折分析(XRD)の結果を図2に示し、TEM像及び粒子径分布を図3にそれぞれ示す。
C13Ag /(C7)2Cu /(C8)3N(銀:銅=5:5、160℃×4時間)の合成
実施例1における反応時間を24時間から4時間に変えたほかは、実施例1と同様に反応させることにより、青紫色粉末(収量0.43g,金属含有率80%、組成比 銀71 mol%:銅29 mol%)を得た。
C13Ag /(C7)2Cu /(C8)3N(銀:銅=5:5、160℃×16時間)の合成
実施例1における反応時間を24時間から16時間に変えたほかは、実施例1と同様に反応させることにより、青紫色粉末(収量0.47g,金属含有率82%,組成比 銀65 mol%:銅35 mol%)を得た。
C13Ag /(C7)2Cu /(C8)3N(銀:銅=5:5、180℃×4時間)の合成
実施例2における反応温度を160℃から180℃に変えたほかは、実施例2と同様に反応させることにより、青紫色粉末(収量0.49g,金属含有率84%,組成比 銀50 mol%,:銅50 mol%,平均粒子径4.0±0.71nm)を得た。得られた粉末のTG/DTA測定による熱重量(TG)変化の結果を図4に示し、X線回折分析(XRD)の結果を図5に示し、TEM像及び粒子径分布を図6にそれぞれ示す。
C7Ag /(C7)2Cu /(C8)3N(銀:銅=5:5、160℃×24時間)の合成
実施例1において用いた脂肪酸銀C13AgをC7Agに変えたほかは、実施例1と同様に反応させることにより青紫色粉末(収量;0.40g、金属含有率;91%、組成比;銀58 mol%,銅42 mol%、平均粒子径5.7±0.79 nm)を得た。得られた粉末のTG/DTA測定による熱重量(TG)変化の結果を図7に示し、X線回折分析(XRD)の結果を図8に示し、TEM像及び粒子径分布を図9にそれぞれ示す。
C17Ag /(C7)2Cu /(C8)3N(銀:銅=5:5、160℃×24時間)の合成
実施例1において用いた脂肪酸銀C13AgをC17Agに変えたほかは、実施例1と同様に反応させることにより青紫色粉末(収量;0.52g,金属含有率83%、組成比 銀58 mol%:銅42 mol%、平均粒子径4.1±2.3nm)を得た。得られた粉末のTG/DTA測定による熱重量(TG)変化の結果を図10に示し、X線回折分析(XRD)の結果を図11に示し、TEM像及び粒子径分布を図12にそれぞれ示す。
C13Ag /(C7)2Cu /(C8)3N(銀:銅=8:2、160℃×24時間)の合成
実施例1において、加えた試薬の量を(C8)3N(2.1 g, 6.0 mmol)と(C7COO)2Cu(0.35g,1.0 mmol)とC13COOAg(1.3 g, 4.0 mmol)に変えたほかは、実施例1と同様に反応させることにより、青紫色粉末(収量0.44g,金属含有率80%,組成比 銀89 mol%:銅11 mol%、平均粒子径4.2±0.49nm)を得た。得られた粉末のTG/DTA測定による熱重量(TG)変化の結果を図13に示し、X線回折分析(XRD)の結果を図14に示し、TEM像及び粒子径分布を図15にそれぞれ示す。
C7Ag /(C7)2Cu /(C8)3N(銀:銅=8:2、160℃×24時間)の合成
実施例5において、加えた試薬の量を(C8)3N(2.1g,6.0mmol)と(C7COO)2Cu(0.35g,1.0mmol)とC7COOAg(1.0g,4.0mmol)に変えたほかは、実施例5と同様に反応させることにより、青紫色粉末(収量0.50g,金属含有率92%、組成比 銀95 mol%:銅5 mol%、平均粒子径8.4±1.4nm)を得た。得られた粉末のTG/DTA測定による熱重量(TG)変化の結果を図16に示し、X線回折分析(XRD)の結果を図17に示し、TEM像及び粒子径分布を図18にそれぞれ示す。
C17Ag /(C7)2Cu /(C8)3N(銀:銅=8:2、160℃×24時間)の合成
実施例6において、加えた試薬の量を(C8)3N(2.1g,6.0mmol)と(C7COO)2Cu(0.35g,1.0mmol)とC17COOAg(1.6g,4.0mmol)に変えたほかは、実施例6と同様に反応させることにより、青紫色粉末(収量0.95g,金属含有率50%,組成比 銀96mol%:銅4 mol%、平均粒子径5.5±1.9nm)を得た。得られた粉末のTG/DTA測定による熱重量(TG)変化の結果を図19に示し、X線回折分析(XRD)の結果を図20に示し、TEM像及び粒子径分布を図21にそれぞれ示す。
C17Ag /(C7)2Cu /(C8)3N(銀:銅=2:8、160℃×24時間)の合成
実施例6において、加えた試薬の量を(C8)3N(3.2g,9.0mmol)と(C7COO)2Cu(1.4g,4.0mmol)とC17COOAg(0.40g,1.0mmol)に変えたほかは、実施例6と同様に反応させることにより、青紫色粉末(収量0.22g,金属含有率99%,組成比 銀41 mol%:銅59 mol%、平均粒子径21±8.9nm)を得た。得られた粉末のX線回折分析(XRD)の結果を図22に示し、TEM像及び粒子径分布を図23にそれぞれ示す。
C13Ag /(C7)2Cu /(C8)3N(銀:銅=5:5、180℃×4時間)の合成
実施例4のスケールを5倍にしたほかは、実施例4と同様に反応させることにより、青紫色粉末(収量2.5g,金属含有率85%、組成比 銀59mol%:銅41mol%、平均粒子径3.9±0.71nm)を得た。得られた粉末のTG/DTA測定による熱重量(TG)変化の結果を図24に示し、X線回折分析(XRD)の結果を図25に示し、TEM像及び粒子径分布を図26にそれぞれ示す。
C13Ag /(C7)2Cu
/(C8)3N/1,2-DDO(銀:銅=5:5、160℃×16時間)の合成
1,2-DDO1.52g(7.5mmol)を添加したほかは、実施例3と同様の条件で熱処理を実施し、青紫色粉末を得た(収量0.585g、金属含有量73%、組成比 銀57mol%:銅43mol%、平均粒子径3.59±0.52nm)。得られた粉末のTG/DTA測定による熱重量(TG)変化の結果を図27に示し、X線回折分析(XRD)の結果を図28に示し、TEM像を図29にそれぞれ示す。
C13Ag /(C7)2Cu
/(C8)3N/1,2-DDO(銀:銅=8:2、160℃×16時間)の合成
実施例12において、加えた試薬の量を1,2-DDO1.21g(6mmol)と(C8)3N(2.12g、6mmol)と(C7COO)2Cu(0.35g、1mmol)とC13COOAg(1.34g、4mmol)に変えたほかは、実施例12と同様にして熱処理を実施し、青紫色粉末を得た(収量0.66g、金属含有量72%、組成比 銀85mol%:銅15mol%、平均粒子径4.23±0.36nm)。得られた粉末のTG/DTA測定による熱重量(TG)変化の結果を図30に示し、X線回折分析(XRD)の結果を図31に示し、TEM像を図32に示す。
C13Ag /(C7)2Cu
/(C8)3N/1,2-DDO(銀:銅=2:8、160℃×16時間)の合成
実施例12において、加えた試薬の量を1,2-DDO1.82g(9mmol)と(C8)3N(3.18g、9mmol)と(C7COO)2Cu(1.40g、4mmol)とC13COOAg(0.335g、1mmol)に変えたほかは、実施例12と同様にして熱処理を実施し、青紫色粉末を得た(収量0.483g、金属含有量78%、組成比 銀26mol%:銅74mol%、平均粒子径5.50±2.73nm)。得られた粉末のTG/DTA測定による熱重量(TG)変化の結果を図33に示し、X線回折分析(XRD)の結果を図34に示し、TEM像を図35に示す。
C13Ag /(C7)2Cu
/(C8)3N/1,2-DDO(銀:銅=5:95、160℃×16時間)の合成
実施例12において、加えた試薬の量を1,2-DDO1.97g(9.75mmol)と(C8)3N(3.45g、9.75mmol)と(C7COO)2Cu(1.66g、4.75mmol)とC13COOAg(0.084g、0.25mmol)に変えたほかは、実施例12と同様にして熱処理を実施し、茶色粉末を得た(収量373mg、金属含有量88%、組成比 銀7mol%:銅93mol%、平均粒子径10.42±5.23nm)。得られた粉末のTG/DTA測定による熱重量(TG)変化の結果を図36に示し、X線回折分析(XRD)の結果を図37に示し、TEM像を図38にそれぞれ示す。
Ag2CO3 /(C7)2Cu
/(C8)3N/ C7COOH(銀:銅=2:8、160℃×24時間)の合成
実施例10において、C17COOAgをAg2CO3(0.138g、0.5mmol)に変え、C7COOH(0.144g、1mmol)を加えたほかは、実施例10と同様にして熱処理を実施し、青紫色粉末を得た(収量0.366g、金属含有量99%、組成比 銀25mol%:銅75mol%、平均粒子径31.4±36.7nm(平均粒子径17.6±3.4nmと120.6±26.5nmが混合))。得られた粉末のX線回折分析(XRD)の結果を図39に示し、TEM像を図40に示す。
また、実施例16において得られたAg/Cu二元金属ナノ粒子のTEM/EDX分析(図40)を行った。粒径の大きな粒子Aと粒径の小さな粒子BにおけるAg/Cu組成比をそれぞれ調べた。その結果を表1に示す。表1の結果からも明らかなように、1つの粒子の中に銀及び銅の両者が含まれていることがわかる。また、銅リッチの粒子(図40、測定点A)と銀リッチの粒子(図40、測定点B)とが混在していることもわかる。さらに、実施例16で得られた粒子(粉末)においては、銀リッチの粒子Aの粒子径が銅リッチBの粒子の粒子径よりも小さくなっており、粒子径によって組成比が異なることがわかる。これは、分解温度が比較的低いAg2CO3が分解した後に、(C7COO)2Cuが分解し、銀と銅の複合化が始まり、銀と銅とが十分に複合する前の小さな粒子径で安定した銀リッチの粒子と、銀と銅とが十分に複合して大きな粒子径で安定した銅リッチの粒子とが形成されると考えられる。
Ag/Cu複合ナノ粒子の焼成膜の特性
実施例11で合成したAg/Cu複合ナノ粒子 C13Ag /(C7)2Cu /(C8)3N(Ag:Cu=5:5、180℃×4時間)に対し、ポリエチレン系分散剤(0.08g)と溶剤にターピネオール(0.25g)を加え、分散性を促進させるためにトルエン数滴を滴下した。トルエンが揮発逸散し、残存しなくなるまで混ぜ、金属含有率65wt%のペーストに調合した。このペーストを用いてスクリーン印刷法により電極パターンを印刷し、大気中350℃×30分間焼成した。その焼成膜Aの表面及び断面のSEM写真を図41及び図42にそれぞれ示す。
別途、同様に印刷して作成した電極パターンを大気中350℃×30分間焼成した後、窒素に3体積%の水素を含む還元性雰囲気下350℃×30分間焼成した。得られた薄膜Bの表面及び断面のSEM写真を図43及び図44にそれぞれ示す。
図41及び図42に示すように、大気中での焼成では、粒子の形状を維持しながら焼結膜を形成していることがわかる。一方、図43及び図44に示すように、大気中での焼成後、さらに窒素に3体積%の水素を含む還元性雰囲気下で焼成すると、ナノ粒子が融着した薄膜が形成されることがわかる。すなわち、比較的低い焼成温度であっても、ナノ粒子の原形をとどめることなく、互いにナノ粒子どうしが融着した内部構造を有する皮膜が得られる。
また、この薄膜Bの電気特性を表2に示す。焼成膜Aのような場合の比抵抗が通常100μΩcm程度であるのに対し、表2からも明らかなように薄膜Bは10μΩcm以下(特に8μΩcm以下)というバルクに匹敵する比抵抗値を示した。このようにAg/Cu複合ナノ粒子を用いたペーストは、配線形成はもとより、高温はんだ代替の接合用としても好適に用いることができる。
Ag/Cu複合ナノ粒子の耐マイグレーション性の検討
イオンマイグレーションとは、高湿高温下で電子回路に電気を流すことで、陽極の金属がイオン化して溶出し、電極間を短絡させる現象である。イオンマイグレーションに対する安定性の検討に用いた電極は、実施例11で合成したC13Ag /(C7)2Cu /(C8)3N(銀:銅=5:5、180℃×4時間)と、同様の条件で合成を行った銀ナノ粒子を用いてそれぞれ形成した。電極の形成は、めのう鉢に分散剤(0.08g)と溶剤にターピネオール(0.25g)を加え、分散性を促進させるためにトルエン数滴を滴下した。さらに前記ナノ粒子を加え、トルエンが揮発逸散し、残存しなくなるまで混ぜ、ペースト化を行った。このペーストを用いてスクリーン印刷法により電極パターンを印刷し、350℃×30分間、窒素に3%の水素を含む還元雰囲気下という焼成条件により電極形成を行った。形成した電極(電極間距離1mm)を使用し、イオンマイグレーションテストを行った。イオンマイグレーションテストはウォータードロップ法により行い、電極間に水を滴下し、電気を流してから電極間を短絡するまでの時間を計測した。その結果を表3に示す。
Claims (11)
- 一般式R1R2R3N(但し、R1~R3は、互いに同一又は異なって、置換基を有していても良いアルキル基又はアリール基を示し、R1~R3は環状につながっていても良い。R1~R3の炭素数は、互いに同一又は異なって1~18である。)で示される3級アミン化合物の存在下、非酸化性雰囲気下で有機銀化合物及び有機銅化合物を含む混合物を150℃以上で熱処理することによって、1つの粒子中に少なくとも銀と銅を含む複合ナノ粒子を得ることを特徴とする複合ナノ粒子の製造方法。
- 有機銀化合物及び有機銅化合物の合計に対する有機銀化合物の仕込みモル比Aに対して、複合ナノ粒子における銀成分及び銅成分の合計に対する銀成分のモル比A’が0.8A≦A’≦1.2Aである、請求項1に記載の製造方法。
- 炭素数5以上の1,2-アルカンジオール及び/又はその誘導体をさらに存在させる、請求項1に記載の製造方法。
- 熱処理温度が250℃以下である、請求項1に記載の製造方法。
- 仕込みモル比Aを1%以上99%以下とする、請求項1に記載の製造方法。
- 有機銀化合物が脂肪酸銀であり、有機銅化合物が脂肪酸銅である、請求項1に記載の製造方法。
- 有機成分を含む複合ナノ粒子であって、1つの粒子中に少なくとも銀と銅を含み、銀が銅よりも多く含まれる組成の粒子と銅が銀よりも多く含まれる組成の粒子とが混在することを特徴とする複合ナノ粒子。
- 複合ナノ粒子における銀成分及び銅成分の合計に対する銀成分のモル比が1%以上99%以下である、請求項7に記載の複合ナノ粒子。
- 耐マイグレーション性配線形成用である、請求項7に記載の複合ナノ粒子。
- 耐マイグレーション性接合用である、請求項7に記載の複合ナノ粒子。
- 請求項7に記載の複合ナノ粒子と、溶剤及び粘度調整用樹脂の少なくとも1種とを含むペースト。
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US13/058,674 US8999206B2 (en) | 2008-08-11 | 2009-08-06 | Composite nanoparticles and manufacturing method thereof |
JP2010524715A JP5707133B2 (ja) | 2008-08-11 | 2009-08-06 | 複合ナノ粒子の製造方法 |
CN200980131359.XA CN102119064B (zh) | 2008-08-11 | 2009-08-06 | 复合纳米粒子及其制造方法 |
DE112009001984.6T DE112009001984B4 (de) | 2008-08-11 | 2009-08-06 | Verbundnanoteilchen und Herstellungsverfahren dafür |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2008207523 | 2008-08-11 | ||
JP2008-207523 | 2008-08-11 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2010018781A1 true WO2010018781A1 (ja) | 2010-02-18 |
Family
ID=41668926
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2009/063961 WO2010018781A1 (ja) | 2008-08-11 | 2009-08-06 | 複合ナノ粒子及びその製造方法 |
Country Status (7)
Country | Link |
---|---|
US (1) | US8999206B2 (ja) |
JP (1) | JP5707133B2 (ja) |
KR (1) | KR101616703B1 (ja) |
CN (1) | CN102119064B (ja) |
DE (1) | DE112009001984B4 (ja) |
TW (1) | TWI461470B (ja) |
WO (1) | WO2010018781A1 (ja) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2018181568A1 (ja) * | 2017-03-28 | 2018-10-04 | 宇部興産株式会社 | 金属複合粒子及びその製造方法、金属複合粒子担持体及びその製造方法、並びに粒子組成物 |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104176701B (zh) * | 2014-08-18 | 2016-08-24 | 中国科学院上海应用物理研究所 | 有机配体包裹的金纳米颗粒薄膜及其场致电子发射装置 |
CN104934330A (zh) * | 2015-05-08 | 2015-09-23 | 京东方科技集团股份有限公司 | 一种薄膜晶体管及其制备方法、阵列基板和显示面板 |
TWI690943B (zh) | 2015-05-20 | 2020-04-11 | 國立大學法人山形大學 | 銀奈米粒子分散體之製造方法、銀奈米粒子墨水之製造方法、電極之製造方法、薄膜電晶體之製造方法及銀奈米粒子墨水 |
US20210162551A1 (en) * | 2017-12-18 | 2021-06-03 | Dic Corporation | Copper fine particle sintered body |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH06128609A (ja) * | 1992-10-15 | 1994-05-10 | Daido Steel Co Ltd | Ag−Cu系合金粉の製造方法 |
JPH10183207A (ja) * | 1996-12-19 | 1998-07-14 | Tomoe Seisakusho:Kk | 超微粒子及びその製造方法 |
JPH11273454A (ja) * | 1998-03-20 | 1999-10-08 | Fukuda Metal Foil & Powder Co Ltd | 導電ペースト用片状銅合金粉の製造方法 |
JP2004273205A (ja) * | 2003-03-06 | 2004-09-30 | Harima Chem Inc | 導電性ナノ粒子ペースト |
JP2006052456A (ja) * | 2004-08-16 | 2006-02-23 | Dowa Mining Co Ltd | fcc構造の合金粒子粉末およびその製造法 |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TWI242478B (en) | 2002-08-01 | 2005-11-01 | Masami Nakamoto | Metal nanoparticle and process for producing the same |
JP2005298921A (ja) | 2004-04-13 | 2005-10-27 | Masami Nakamoto | 複合金属超微粒子及びその製造方法 |
JP2006152353A (ja) * | 2004-11-26 | 2006-06-15 | Kobe Steel Ltd | 抗菌薄膜 |
JP5753338B2 (ja) * | 2005-07-01 | 2015-07-22 | ナショナル ユニヴァーシティー オブ シンガポール | 導電性複合材料 |
JP4662829B2 (ja) | 2005-08-29 | 2011-03-30 | 地方独立行政法人 大阪市立工業研究所 | 銀ナノ粒子及びその製造方法 |
JP4812370B2 (ja) | 2005-08-29 | 2011-11-09 | 地方独立行政法人 大阪市立工業研究所 | 貴金属ナノ粒子の製造方法 |
JP5080731B2 (ja) * | 2005-10-03 | 2012-11-21 | 三井金属鉱業株式会社 | 微粒銀粒子付着銀銅複合粉及びその微粒銀粒子付着銀銅複合粉製造方法 |
KR100836659B1 (ko) * | 2006-07-06 | 2008-06-10 | 삼성전기주식회사 | 금속 및 금속 산화물 나노입자의 제조방법 |
US7460046B2 (en) * | 2006-12-22 | 2008-12-02 | Infineon Technologies Ag | Sigma-delta modulators |
US8382878B2 (en) * | 2008-08-07 | 2013-02-26 | Xerox Corporation | Silver nanoparticle process |
JP5105332B2 (ja) * | 2008-08-11 | 2012-12-26 | 昭和電工株式会社 | 磁気記録媒体、その製造方法および磁気記録再生装置 |
CN101608077A (zh) * | 2009-07-16 | 2009-12-23 | 复旦大学 | 一种纳米铜导电墨水的制备方法 |
-
2009
- 2009-08-06 JP JP2010524715A patent/JP5707133B2/ja active Active
- 2009-08-06 WO PCT/JP2009/063961 patent/WO2010018781A1/ja active Application Filing
- 2009-08-06 KR KR1020117005485A patent/KR101616703B1/ko active IP Right Grant
- 2009-08-06 DE DE112009001984.6T patent/DE112009001984B4/de not_active Expired - Fee Related
- 2009-08-06 US US13/058,674 patent/US8999206B2/en not_active Expired - Fee Related
- 2009-08-06 CN CN200980131359.XA patent/CN102119064B/zh not_active Expired - Fee Related
- 2009-08-06 TW TW098126543A patent/TWI461470B/zh not_active IP Right Cessation
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH06128609A (ja) * | 1992-10-15 | 1994-05-10 | Daido Steel Co Ltd | Ag−Cu系合金粉の製造方法 |
JPH10183207A (ja) * | 1996-12-19 | 1998-07-14 | Tomoe Seisakusho:Kk | 超微粒子及びその製造方法 |
JPH11273454A (ja) * | 1998-03-20 | 1999-10-08 | Fukuda Metal Foil & Powder Co Ltd | 導電ペースト用片状銅合金粉の製造方法 |
JP2004273205A (ja) * | 2003-03-06 | 2004-09-30 | Harima Chem Inc | 導電性ナノ粒子ペースト |
JP2006052456A (ja) * | 2004-08-16 | 2006-02-23 | Dowa Mining Co Ltd | fcc構造の合金粒子粉末およびその製造法 |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2018181568A1 (ja) * | 2017-03-28 | 2018-10-04 | 宇部興産株式会社 | 金属複合粒子及びその製造方法、金属複合粒子担持体及びその製造方法、並びに粒子組成物 |
JPWO2018181568A1 (ja) * | 2017-03-28 | 2019-04-04 | 宇部興産株式会社 | 金属複合粒子の製造方法、金属複合粒子担持体の製造方法、及び粒子組成物 |
Also Published As
Publication number | Publication date |
---|---|
KR101616703B1 (ko) | 2016-04-29 |
TWI461470B (zh) | 2014-11-21 |
KR20110059714A (ko) | 2011-06-03 |
DE112009001984B4 (de) | 2017-10-12 |
JP5707133B2 (ja) | 2015-04-22 |
CN102119064A (zh) | 2011-07-06 |
JPWO2010018781A1 (ja) | 2012-01-26 |
US20110193033A1 (en) | 2011-08-11 |
TW201011063A (en) | 2010-03-16 |
DE112009001984T5 (de) | 2011-06-30 |
CN102119064B (zh) | 2015-04-01 |
US8999206B2 (en) | 2015-04-07 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5707134B2 (ja) | 銅系ナノ粒子の製造方法 | |
US7648554B2 (en) | Metal nanoparticles and method for manufacturing same | |
EP2671655B1 (en) | Method for manufacturing coated metal fine particles | |
JP5580562B2 (ja) | 銀−銅系混合粉末及びそれを用いた接合方法 | |
JP5620122B2 (ja) | 接合用材料及び接合方法 | |
JP4812370B2 (ja) | 貴金属ナノ粒子の製造方法 | |
JP4662829B2 (ja) | 銀ナノ粒子及びその製造方法 | |
JP5707133B2 (ja) | 複合ナノ粒子の製造方法 | |
KR101671049B1 (ko) | 니켈-코발트 나노 입자 및 그 제조 방법 | |
JP2011068936A (ja) | 銀コア銀銅合金シェルナノ微粒子とその微粒子被着物及びその焼結被着物 | |
JP2010209407A (ja) | 金属微粒子の製造方法 | |
JP2007095509A (ja) | 導電性ペースト | |
JP6163021B2 (ja) | 複合微粒子の製造方法 | |
JP2007095527A (ja) | 導電性ペーストおよびその製造方法 | |
Park et al. | Oxidation Stability of Conductive Copper Paste Prepared through Electron Beam Irradiation | |
KR102240015B1 (ko) | 용액공정을 이용한 구리 나노입자 제조방법 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 200980131359.X Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 09806673 Country of ref document: EP Kind code of ref document: A1 |
|
DPE1 | Request for preliminary examination filed after expiration of 19th month from priority date (pct application filed from 20040101) | ||
WWE | Wipo information: entry into national phase |
Ref document number: 2010524715 Country of ref document: JP |
|
ENP | Entry into the national phase |
Ref document number: 20117005485 Country of ref document: KR Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 13058674 Country of ref document: US |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 09806673 Country of ref document: EP Kind code of ref document: A1 |