WO2012147945A1 - Particule d'argent tabulaire, procédé de fabrication associé, colle utilisant celle-ci et circuit imprimé utilisant la colle - Google Patents

Particule d'argent tabulaire, procédé de fabrication associé, colle utilisant celle-ci et circuit imprimé utilisant la colle Download PDF

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Publication number
WO2012147945A1
WO2012147945A1 PCT/JP2012/061448 JP2012061448W WO2012147945A1 WO 2012147945 A1 WO2012147945 A1 WO 2012147945A1 JP 2012061448 W JP2012061448 W JP 2012061448W WO 2012147945 A1 WO2012147945 A1 WO 2012147945A1
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WIPO (PCT)
Prior art keywords
sem
silver
fine particles
silver fine
organic substance
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Ceased
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PCT/JP2012/061448
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English (en)
Japanese (ja)
Inventor
太郎 中野谷
崇 樋之津
宏敏 齋藤
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Dowa Electronics Materials Co Ltd
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Dowa Electronics Materials Co Ltd
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Priority to TW104133555A priority Critical patent/TWI530964B/zh
Priority to JP2013512485A priority patent/JP5969988B2/ja
Priority to TW101115136A priority patent/TWI530963B/zh
Publication of WO2012147945A1 publication Critical patent/WO2012147945A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
    • 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
    • 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
    • B22F1/0551—Flake form nanoparticles
    • 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
    • B22F1/056—Submicron particles having a size above 100 nm up to 300 nm
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
    • B22F1/102—Metallic powder coated with organic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • 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
    • 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
    • H05K1/097—Inks comprising nanoparticles and specially adapted for being sintered at low temperature
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F77/00—Constructional details of devices covered by this subclass
    • H10F77/20—Electrodes
    • H10F77/206—Electrodes for devices having potential barriers
    • H10F77/211—Electrodes for devices having potential barriers for photovoltaic cells

Definitions

  • the present invention relates to a flat silver fine particle suitably used for fine wiring, a bonded body, and the like, a manufacturing method thereof, a paste containing the particle, and a printed circuit using the paste.
  • conductive paste in which silver particles are dispersed in an organic medium has been used to form electrodes and circuits of electronic components.
  • the silver particles used in the conductive paste flat silver particles having a large contact area between the silver particles are suitably used (see, for example, Patent Document 1).
  • Patent Document 2 discloses tabular silver fine particles obtained by a wet reaction.
  • Patent Document 2 As a technique for obtaining silver fine particles having a flat plate shape by a simple process, the method described in Patent Document 2 can be exemplified as described above. However, in order to obtain a film having conductivity with the obtained fine particles, heating of 250 ° C. is required. It is known that the silver fine particles can lower the melting point if they are miniaturized, but if heating at this temperature is required, it cannot be said that the effect of miniaturizing silver can be fully enjoyed. As a result, there is a problem that the types of substrates on which the metal wiring is formed are limited. Accordingly, there is a need to provide a paste that exhibits conductivity at a lower temperature.
  • the present invention has been made in view of such problems of the prior art, and an object of the present invention is to provide a conductive paste that exhibits a low resistance value even when heat treatment is performed at a low temperature of about 200 ° C. is there.
  • the present inventors have conducted extensive research, and as a result, obtained are the following tabular silver fine particles, a method for producing tabular silver fine particles, and a conductive paste containing the tabular silver fine particles. It has been found that the above problems can be solved by using it.
  • the particles according to the present invention are tabular silver fine particles, and an organic substance having 2 to 10 carbon atoms is attached to the surface thereof.
  • the average value of the particle diameter in the thickness direction calculated from the SEM image (hereinafter referred to as d SEM). to as -T) is 10 ⁇ 200 nm, the ratio of the longitudinal average particle diameter (d SEM-L) and the average value of the particle diameter of the thickness direction (d SEM-T) (d SEM-L / D SEM-T ) having an aspect ratio of 2 to 100.
  • the method for producing tabular silver fine particles according to the present invention comprises adding a water-soluble silver compound, a water-soluble complexing agent, an organic substance having 3 to 10 carbon atoms, and a reducing agent composed of an organic substance to water to form a tabular form. It is characterized by producing silver fine particles.
  • the method for producing tabular silver fine particles is characterized by adding citric acid or a derivative thereof.
  • the reducing agent made of an organic substance is ascorbic acid or a derivative or isomer thereof.
  • the conductive paste according to the present invention is characterized by containing the flat silver particles.
  • the conductive paste has an average value of the particle diameter in the longitudinal direction calculated from the SEM image (hereinafter referred to as D SEM-L ) together with the above-mentioned plate-like silver fine particles of 2.5 to 15.0 ⁇ m. And silver particles in a range of 3 to 50 times the d SEM-L of the tabular silver fine particles are mixed.
  • the shape of the silver particles is a flat plate.
  • the tabular silver fine particles in the present invention cover the surface with an organic substance having 2 to 10 carbon atoms. If it coat
  • the organic substance covering the surface is preferably an organic substance having 2 to 8 carbon atoms, more preferably 2 to 6 carbon atoms. Moreover, even if it is an organic substance with few carbon numbers, if the coating amount increases, the above-described problem that the resistance value cannot be lowered occurs.
  • the coating amount is 3.0% by mass or less and preferably 0.1% by mass or more, preferably 2.0% by mass or less and 0.1% by mass or more, more preferably 1.0% by mass or less and 0.1% by mass. % Or more.
  • the flat silver fine particles in the present invention have a d SEM-T of 10 to 200 nm.
  • d SEM-T is more preferably 10 to 190 nm.
  • the “longitudinal size” means the longest observed length among the diagonal lines of the plate surface portion in the plate shape.
  • the tabular silver fine particles in the present invention preferably have a particle aspect ratio (d SEM-L / d SEM-T ) of 2 to 100, and more preferably 3 to 50.
  • d SEM-L / d SEM-T particle aspect ratio
  • the filling property in the coating film is improved and effective in reducing the specific resistance.
  • an increase in the contact area is effective in reducing the contact resistance.
  • the flat silver fine particles have a d SEM-L of 60 to 2,000 nm, more preferably 105 to 1,900 nm.
  • the method for producing tabular silver fine particles in the present invention employs a wet reduction method, and is formed into a plate shape by a silver ion dispersion liquid preparation step, a silver reduction step, a silver particle washing step, and a silver particle drying step. Silver fine particles are obtained. Below, the manufacturing method of the silver fine particle in this invention is demonstrated in detail.
  • Silver compound This reaction is preferably carried out in water from the viewpoint of cost and safety, and the silver compound as a raw material is preferably water-soluble from the viewpoint of the uniformity of the reaction.
  • silver nitrate, silver acetate and the like can be exemplified as the silver compound showing solubility in water, but silver nitrate is preferable from the viewpoint of ease of dissolution.
  • a solution in which silver itself is dissolved with an acid may be used.
  • the complexing agent is a compound that combines with metal ions to form complex ions.
  • a complexing agent tabular silver fine particles can be stably produced.
  • complexing agents include citric acid, tartaric acid, gluconic acid, succinic acid, malonic acid, succinic acid, glutaric acid, adipic acid, malic acid, fumaric acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid
  • Complexing agents such as carboxylic acids or oxycarboxylic acids such as EDTA (ethylenediaminetetraacetic acid), DTPA (diethylenetriaminepentaacetic acid), IDA (iminoniacetic acid), NTA (nitrilotriacetic acid), etc.
  • EDTA ethylenediaminetetraacetic acid
  • DTPA diethylenetriaminepentaacetic acid
  • IDA iminoniacetic acid
  • NTA nitrilotriacetic acid
  • the organic substance having 3 to 10 carbon atoms serves as a steric hindrance of the silver fine particles that are reduced and deposited, and prevents the particles from aggregating.
  • the number of carbon atoms is 1 or 2, the function as steric hindrance is not sufficient, and the particles become coarse.
  • the number of carbon atoms exceeds 10, it is difficult to thermally decompose the organic substance at a low temperature, which is not preferable because the resistance value cannot be lowered sufficiently when formed into a conductive film.
  • it is an organic substance having 3 to 8 carbon atoms, more preferably 3 to 6 carbon atoms.
  • silver fine particles are obtained by adding a reducing agent to the silver ion dispersion prepared in the liquid preparation step.
  • the reducing agent used in this step will be described in detail.
  • a reducing agent having a weak reducing power In order to obtain uniform tabular grains, it is necessary to use a reducing agent having a weak reducing power.
  • a reducing agent made of an organic material is preferable. More specifically, formic acid, oxalic acid, ascorbic acid, acetaldehyde, which are organic substances having an aldehyde group, glucose (glucose), fructose (fructose), monosaccharides, maltose (malt sugar), cellobiose, fructose, which are disaccharides Can be exemplified.
  • Silver fine particle recovery and washing process Since the silver fine particles obtained through the reduction step contain an excessive organic substance that is not coated, it is necessary to wash the organic substance after collecting the particles. It is preferable to use pure water as the cleaning solvent. As a method of recovery and washing, decantation, filter press, etc. can be raised, but not limited thereto.
  • the temperature is preferably 100 ° C. or lower, and more preferably 80 ° C. or lower. If too much heat is applied, particles are sintered at the time of drying, which is not preferable.
  • the produced plate-like silver fine particles were subjected to the evaluation of the coating amount, the carbon number of the coating, and the particle diameter by the following methods.
  • the silver fine particles are placed in an ashtray for ash measurement (square 50 ⁇ 30 ⁇ 10 mm) so as to have a thickness of 1 to 2 mm, and the ashtray for ash measurement is placed in a muffle furnace (FO310 manufactured by Yamato Scientific Co., Ltd. ) And calculated from the mass before and after the firing.
  • the firing conditions are such that the temperature is raised from 25 ° C. to 700 ° C. at a rate of temperature rise of 10 ° C./min in the air, and then naturally cooled and cooled to room temperature.
  • the carbon number of the coating was determined by, for example, subjecting the obtained silver particles to GC-MS and confirming the organic component.
  • a gas component obtained by heating and vaporizing silver particles at 350 ° C. under a helium atmosphere using a GC-MS apparatus (7890A GC System and 5975C inert XL EI / CI MSD manufactured by Agilent Technologies Inc.) Were separated and collected using a column (DB-5HT 123-5731, flow rate 2.0 ml / min, manufactured by J & W Scientific), and the coating was evaluated.
  • the particle diameter calculation method in the longitudinal direction and the thickness direction is as follows.
  • the particle surface was observed using a scanning electron microscope (S-4700 manufactured by Hitachi High-Technologies Corporation).
  • the magnification in observation was 30,000 times when the particle size was approximately 500 nm or less, 10,000 times when the particle size was 500 to 2,000 nm, and 3,000 times when the particle size was 2,000 nm or more.
  • image analysis software A image-kun (registered trademark) manufactured by Asahi Kasei Engineering Co., Ltd.).
  • the silver particles are characterized by using the flat silver particles described in the present invention. Moreover, although the silver particle produced by the well-known method may be mixed and used, as a shape of the silver particle generally mixed, a flat silver particle is preferable.
  • the silver particles to be mixed preferably have a D SEM-L of 2.5 to 15.0 ⁇ m and 3 to 50 times the d SEM-L of the tabular silver fine particles described in the present invention. More preferably, D SEM-L is 3.0 to 10.0 ⁇ m, and 5 to 20 times the d SEM-L of the plate-like silver fine particles.
  • the dispersion medium used for the conductive paste in the present invention is preferably a polar solvent. If a polar solvent is selected, the vapor pressure is low, which is suitable for handling. There is no problem if one having a property compatible with various resins is used, but an organic solvent such as ester, ether, ketone, ether ester, alcohol, hydrocarbon or amine is used. Is preferred.
  • Dispersant You may add the dispersing agent which disperse
  • the property is not particularly limited as long as it has an affinity for the particle surface and also has an affinity for the dispersion medium, and may be a commercially available one. For example, not only a single type but also a combination may be used.
  • This addition amount is 3.0% by mass or less, preferably 1.0% by mass or less, more preferably 0.5% by mass or less, based on the mass of the silver particles.
  • thermosetting resin can be selected from phenol resin, epoxy resin, unsaturated polyester resin, isocyanate compound, melamine resin, urea resin, silicone resin, and the like.
  • thermoplastic resin it can select from an acrylic resin, a polyester resin, a polyurethane resin, etc.
  • the addition amount of the resin is 2 to 20% by mass, preferably 2 to 15% by mass, based on the mass of the silver particles. If the amount of resin to be added is too large, the resin remains in the wiring more than necessary after firing, which is not preferable because it has a great influence on the conductivity. On the other hand, if the addition amount is reduced, the adhesion between the wiring and the substrate cannot be ensured.
  • thermosetting epoxy resin is often used for the conductive paste, and among the epoxy resins, a polyvalent epoxy compound is preferable from the viewpoint of enhancing storage stability.
  • a polyvalent epoxy resin a glycidyl type epoxy resin having an overwhelmingly high productivity is preferable, and more preferably an epoxy resin obtained by glycidylating polyhydric phenols because of excellent adhesion and heat resistance of a cured product. Is preferred. More preferably, it is a bisphenol type epoxy resin, and in particular, an epoxy resin obtained by glycidylating bisphenol A and an epoxy resin obtained by glycidylating bisphenol F are preferred.
  • the resin is preferably in a liquid form.
  • the epoxy equivalent is preferably 300 or less. When the epoxy equivalent is a value larger than 300, the composition becomes solid, the resistance value becomes high, and handling is inconvenient when used, which is not preferable.
  • the type of curing agent may be a commercially available one. Moreover, you may use together not only a single kind.
  • the curing agent include amine curing agents, acid anhydride curing agents, imidazoles, Lewis acids, Bronsted acids, and phenol resins.
  • ⁇ Manufacture of conductive paste Components such as silver particles, a dispersion medium, and a resin are mixed and then introduced into a kneading defoaming machine to form a kneaded product of the components. Thereafter, a paste is formed by performing a mechanical dispersion treatment in some cases.
  • any known method can be employed under the condition that the mechanical dispersion treatment is not accompanied by significant modification of silver particles.
  • an ultrasonic dispersion, a disper, a three roll mill, a ball mill, a bead mill, a twin screw kneader, a self-revolving stirrer and the like can be exemplified, and these can be used alone or in combination.
  • the surface resistance of the conductive film was measured with a four-terminal type resistivity meter (Loresta GP MCP-T610 type manufactured by Mitsubishi Chemical Corporation), and the thickness of the conductive film was measured with a surface roughness meter (Surfcom 1500D type manufactured by Tokyo Seimitsu Co., Ltd.)
  • the patterns shown in FIG. 1 are spaced apart from (1) 300 ⁇ m, (2) 500 ⁇ m, (3) 1,000 ⁇ m, and (4) 2,000 ⁇ m, respectively.
  • the contact resistance was calculated. Specifically, the half of the Y-intercept of the graph obtained when the interval between the patterns is taken on the horizontal axis and the measured resistance value is taken on the vertical axis was taken as the contact resistance.
  • Example 1> (Method for producing silver fine particles A) 51.0 g of silver nitrate crystals (special grade product manufactured by Toyo Chemical Co., Ltd.) as a silver compound and citric acid monohydrate (manufactured by Wako Pure Chemical Industries, Ltd.) as a complexing agent for 1,000 g of pure water 50.2 g and potassium sorbate (special grade product manufactured by Wako Pure Chemical Industries, Ltd.) 7.7 g as an organic material for coating, and then heated to 50 ° C. to obtain a silver ion dispersion.
  • silver nitrate crystals special grade product manufactured by Toyo Chemical Co., Ltd.
  • citric acid monohydrate manufactured by Wako Pure Chemical Industries, Ltd.
  • potassium sorbate special grade product manufactured by Wako Pure Chemical Industries, Ltd.
  • the reducing agent dispersion was added at a rate of 33 ml / min using a quantitative feed pump (RP-2100, manufactured by Tokyo Science Instruments Co., Ltd.) while stirring the silver ion dispersion. Thereafter, the liquid temperature was kept at 50 ° C. and kept for 60 minutes to obtain silver fine particles.
  • RP-2100 manufactured by Tokyo Science Instruments Co., Ltd.
  • the obtained silver fine particles were subjected to suction filtration while flowing pure water, thereby washing the particles and removing excess impurities. Thereafter, vacuum drying was performed at 30 ° C. for 12 hours to obtain a dry powder of silver fine particles.
  • the production method and characteristics of the silver fine particles A are shown in Table 1.
  • the silver fine particles (B to I) thereafter are also shown in Table 1.
  • the GC-MS spectrum result of the dried powder is shown in FIG.
  • the observed peak was confirmed to be acetic acid.
  • the horizontal axis is time (seconds), and the vertical axis is abundance.
  • Example 2> (Method for producing silver fine particles B) The same procedure as in the case of silver fine particles A was performed except that 4.2 g of 60% by mass nitric acid (special grade product manufactured by Wako Pure Chemical Industries, Ltd.) was added to the silver ion dispersion for the purpose of pH adjustment.
  • nitric acid special grade product manufactured by Wako Pure Chemical Industries, Ltd.
  • Example 3> (Method for producing silver fine particles C) The same procedure as in the case of silver fine particles A was performed, except that 10.5 g of 60% by mass nitric acid (special grade manufactured by Wako Pure Chemical Industries, Ltd.) was added to the silver ion dispersion for the purpose of pH adjustment.
  • nitric acid special grade manufactured by Wako Pure Chemical Industries, Ltd.
  • Example 4> (Method for producing silver fine particles D) The reaction was carried out in an air atmosphere, and the same operation as in the case of silver fine particles A was performed except that the retention time after addition of the reducing agent was 3 hours.
  • Example 5> (Method for producing silver fine particles E) The same thing as the case of the silver fine particles A was performed except that the additive was changed from potassium sorbate to gallic acid hydrate (special grade manufactured by Tokyo Chemical Industry Co., Ltd.).
  • Example 11 1.9 g of terpineol (special grade manufactured by Wako Pure Chemical Industries, Ltd.) as a dispersion solvent, 0.1 g of a polymer pigment dispersant Ajisper PA-111 (Ajinomoto Fine Techno Co., Ltd.) as a dispersant, bisphenol F type as a resin 4.6 g of epoxy resin JER807 (manufactured by Mitsubishi Chemical Corporation) and 0.2 g of boron trifluoride monoethylamine complex (manufactured by Wako Pure Chemical Industries, Ltd.) as a curing agent were added and mixed. Further, 93.2 g of silver fine particles A were mixed, and then stirred for 30 seconds with a self-revolving vacuum stirring mixer (V-mini300 manufactured by EME Co., Ltd.).
  • V-mini300 self-revolving vacuum stirring mixer
  • the mixture thus obtained was passed five times with a three roll (EXAKT, M-80S type manufactured by Apartabaus) to prepare a conductive paste.
  • the obtained conductive paste was printed on a substrate and heat-treated at 200 ° C. for 60 minutes to form a conductive film.
  • the specific resistance was 17.3 ⁇ ⁇ cm and the contact resistance was 0.161 ⁇ .
  • a conductive film having low specific resistance and contact resistance was obtained.
  • Example 11 was repeated except that the silver fine particles used were changed to silver fine particles G. As a result, the specific resistance of the obtained conductive film was 35.1 ⁇ ⁇ cm, and the contact resistance was 0.166 ⁇ .
  • Example 11 was repeated except that the silver fine particles used were changed to silver fine particles H.
  • the specific resistance of the obtained conductive film was 32.6 ⁇ ⁇ cm, and the contact resistance was 0.231 ⁇ .
  • the tabular silver fine particles obtained by the present invention may be made into a paste alone, but a paste having low specific resistance and contact resistance can be obtained by mixing with known silver particles. Then, the Example about the mixed paste with a well-known silver particle is described.
  • Known silver particles (silver particles I to L) used for mixing are shown in Table 2 (D SEM-L is the average value of the particle diameter in the longitudinal direction calculated from the SEM image, and D SEM-T is the SEM)
  • the average value of the particle diameter in the thickness direction calculated from the image and the aspect ratio are values calculated by D SEM-L / D SEM-T ).
  • D SEM-L is the average value of the major axis length of the particle calculated from the SEM image
  • D SEM-T is the average value of the minor axis length calculated from the SEM image. Represents.
  • Example 12 the silver powder used was a combination shown in Table 3, and in Example 11, the amount of silver fine particles A was 93.2 g, and the total amount of silver fine particles and silver particles was 46.6 g in total. Example 11 was repeated except that 93.2 g.
  • the specific resistance and contact resistance obtained are shown in Table 3.
  • Example 11 was repeated except that the silver powder used was changed to the silver powder (one type of silver particle) shown in Table 3. The specific resistance and contact resistance obtained are shown in Table 3.
  • Example 11 was repeated except that the silver powder used was a combination shown in Table 3 and the mixed amount of the silver powder was 46.6 g each, for a total of 93.2 g.
  • the obtained specific resistance and contact resistance are shown in Table 3.
  • FIG. 4 is a graph showing the relationship between specific resistance and contact resistance.
  • the vertical axis represents contact resistance ( ⁇ ), and the horizontal axis represents specific resistance ( ⁇ ⁇ cm).
  • the horizontal axis is a logarithmic axis.
  • Black diamonds are examples, and white squares are comparative examples. In the black diamond example, both specific resistance and contact resistance were low, but in the white square comparative example, either one or both characteristics were high.
  • tabular silver fine particles and conductive paste containing silver fine particles can be obtained, and a conductive film having good specific resistance and contact resistance can be obtained at a processing temperature of about 200 ° C. It was.
  • This can be suitably used for wiring drawing and electrode formation in fields such as solar cells, capacitors, and RFIDs.

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  • Chemical & Material Sciences (AREA)
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  • Nanotechnology (AREA)
  • Inorganic Chemistry (AREA)
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Abstract

L'invention concerne une colle conductrice qui présente une faible résistance même avec un traitement thermique à basse température d'environ 200°C. L'invention concerne également une particule d'argent tabulaire, selon laquelle : une matière organique présentant un nombre de carbones de 2-10 est fixée sur la surface de celle-ci ; et le diamètre de particule moyen dans le sens de l'épaisseur calculé avec une image SEM (ci-après désigné dSEM-T) est de 10-200 nm. La particule d'argent est caractérisée en ce qu'elle présente un rapport d'aspect, qui est le rapport (dSEM-L/dSEM-T) entre le diamètre de particule moyen dans le sens de la longueur (dSEM-L) et le dSEM-T, de 2-100.
PCT/JP2012/061448 2011-04-28 2012-04-27 Particule d'argent tabulaire, procédé de fabrication associé, colle utilisant celle-ci et circuit imprimé utilisant la colle Ceased WO2012147945A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
TW104133555A TWI530964B (zh) 2011-04-28 2012-04-27 Sheet-like silver microparticles and methods for producing the same, and a paste using the same and a paste
JP2013512485A JP5969988B2 (ja) 2011-04-28 2012-04-27 平板状の銀微粒子とその製造方法およびそれを用いたペーストとペーストを用いた印刷回路の製造方法
TW101115136A TWI530963B (zh) 2011-04-28 2012-04-27 Sheet-like silver microparticles and methods for producing the same, and a paste using the same and a paste

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2011-100657 2011-04-28
JP2011100657 2011-04-28

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WO2012147945A1 true WO2012147945A1 (fr) 2012-11-01

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US12125607B2 (en) 2016-04-04 2024-10-22 Nichia Corporation Metal powder sintering paste and method of producing the same, and method of producing conductive material
JP2018168226A (ja) * 2017-03-29 2018-11-01 三菱マテリアル株式会社 ペースト状銀粉組成物、接合体の製造方法および銀膜の製造方法
WO2024070271A1 (fr) * 2022-09-27 2024-04-04 ナミックス株式会社 Composition conductrice, compact fritté de celle-ci, structure stratifiée, pièce électronique et dispositif à semi-conducteur

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