WO2009116185A1 - Pâte de nanoparticules d'argent composites, son procédé de production, procédé de connexion et procédé de formation de motifs - Google Patents

Pâte de nanoparticules d'argent composites, son procédé de production, procédé de connexion et procédé de formation de motifs Download PDF

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Publication number
WO2009116185A1
WO2009116185A1 PCT/JP2008/062238 JP2008062238W WO2009116185A1 WO 2009116185 A1 WO2009116185 A1 WO 2009116185A1 JP 2008062238 W JP2008062238 W JP 2008062238W WO 2009116185 A1 WO2009116185 A1 WO 2009116185A1
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WIPO (PCT)
Prior art keywords
silver
composite
paste
composite silver
resin
Prior art date
Application number
PCT/JP2008/062238
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English (en)
Japanese (ja)
Inventor
小松　晃雄
Original Assignee
株式会社応用ナノ粒子研究所
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Publication date
Application filed by 株式会社応用ナノ粒子研究所 filed Critical 株式会社応用ナノ粒子研究所
Priority to JP2010503736A priority Critical patent/JP5306322B2/ja
Priority to CN2008801281306A priority patent/CN101990474B/zh
Priority to US12/735,435 priority patent/US8348134B2/en
Priority to PCT/JP2008/073660 priority patent/WO2009090846A1/fr
Priority to KR1020107017975A priority patent/KR101222304B1/ko
Priority to EP08870788.0A priority patent/EP2298471B1/fr
Priority to JP2009549977A priority patent/JP4680313B2/ja
Priority to PCT/JP2008/073751 priority patent/WO2009090849A1/fr
Publication of WO2009116185A1 publication Critical patent/WO2009116185A1/fr
Priority to US13/707,298 priority patent/US8459529B2/en
Priority to US13/707,384 priority patent/US8906317B2/en

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    • 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
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Definitions

  • the present invention relates to a paste composed of composite silver nanoparticles in which an organic coating layer made of an organic substance is formed around a silver nucleus made of a large number of silver atoms. More specifically, the paste is applied and fired.
  • the present invention relates to a composite silver nanopaste in which the organic coating layer and other organic components are diffused to form a silver film, and a semiconductor junction and an electrode pattern are formed from the silver film, a manufacturing method thereof, a bonding method, and a pattern formation method.
  • solder is an alloy of Sn and Pb, and the use of Pb is being prohibited as a recent environmental preservation measure. Therefore, development of a Pb-free alternative solder that replaces the conventional solder is desired.
  • Patent Document 1 Japanese Patent No. 3205793 was published as Patent Document 1.
  • Silver organic compounds (especially silver organic complexes) were selected as starting materials.
  • the silver organic compound is heated at a temperature higher than or equal to the decomposition start temperature and lower than the complete decomposition temperature in an inert gas atmosphere in which air is shut off, and the coating layer of the silver organic compound is formed around the decomposed and reduced silver core.
  • Composite silver nanoparticles were produced.
  • the particle size of silver nuclei is 1 to 100 nm, and is therefore commonly referred to as composite silver nanoparticles. Specifically, when 100 g of silver stearate was heated at 250 ° C. for 4 hours in a flask under a nitrogen stream, composite silver nanoparticles having a silver nucleus with a particle size of 5 nm were generated.
  • Patent Document 2 The inventor is one of the inventors of this international publication. A plurality of inventions are disclosed in this publication, and among them, a method of treating a metal inorganic compound with a surfactant is important. That is, a first step of colloiding a metal inorganic compound with a surfactant in a non-aqueous solvent to form an ultrafine particle precursor, and a reducing agent is added to the colloidal solution to reduce the ultrafine particle precursor. And a second step of generating composite metal nanoparticles in which a surfactant shell is formed as a coating layer on the outer periphery of the metal core.
  • the above-described method has a feature that since the metal inorganic compound is dissolved in a non-aqueous solvent, the produced composite metal nanoparticles are dispersed in the non-aqueous solvent and are not likely to be in a dumpling state.
  • the added surfactant has a large number of carbon atoms, the number of carbon atoms in the surfactant shell, which is an organic coating layer, is naturally large, and the temperature at which the surfactant shell is baked to disperse, that is, the firing temperature is increased. was there.
  • Patent Document 3 it is described that composite silver nanoparticles are made from silver carbonate and myristic acid (C number is 14). Further, it is described that composite silver nanoparticles were produced from silver carbonate and stearyl alcohol (C number is 18). However, since myristic acid (C number is 14) and stearyl alcohol (C number is 18) have a large carbon number, it goes without saying that there is a disadvantage that the firing temperature for silvering becomes high.
  • the present inventors react silver carbonate with C1-C9 or C11 alcohol to produce silver alkoxide-type composite silver nanoparticles consisting of alcohol residues around the silver nucleus. Succeeded.
  • the C1 to C9 or C11 composite silver nanoparticles obtained in this way are naturally lower in silvering temperature than the C14 or C18 composite silver nanoparticles obtained in Patent Document 3.
  • As a result of the decrease in the number of carbon atoms there is an advantage that the silver content increases while the silvering temperature decreases.
  • the present inventors decided to prepare a paste using the composite silver nanoparticles of C1 to C9 or C11.
  • This paste is used to assemble the electronic parts by joining the materials, or to test the formation of the electrode pattern on the substrate to confirm the effectiveness of the paste.
  • the bonding method using paste there are the following two conventional patent publications.
  • Patent Document 4 composite metal ultrafine particles in which the periphery of a core portion substantially composed of a metal component having an average particle diameter of 1 to 10 nm is coated with a coating layer composed of an organic substance having 5 or more carbon atoms are prepared in advance, and the composite Preparing a metal paste by dispersing metal ultrafine particles in a solvent, attaching the metal paste onto a terminal electrode of a circuit board to form a metal paste ball mainly composed of composite metal ultrafine particles, and the metal There are described a step of bonding electrodes of a semiconductor element on a paste ball using a face-down method and a step of electrically connecting the semiconductor element and a circuit board by low-temperature firing.
  • Japanese Patent No. 3638487 is disclosed.
  • composite metal ultrafine particles in which the periphery of a core portion substantially composed of a metal component having an average particle diameter of 1 to 10 nm is coated with a coating layer composed of an organic substance having 5 or more carbon atoms are prepared in advance.
  • a process of forming a solder bump and a process of heat-sealing the solder bump to a terminal electrode of a circuit board are disclosed.
  • Patent Documents 4 and 5 describe that composite metal ultrafine particles are dispersed in a solvent to prepare a metal paste.
  • claim 3 of Patent Document 4 includes a metal having high conductivity in addition to a solvent.
  • a metal paste to which a resin component is added is described.
  • only toluene is exemplified as a solvent, and the roles of Patent Documents 4 and 5 are imparted with a role of reducing the viscosity to make the paste into a solution.
  • the resin component is added to increase the viscosity, and an appropriate amount of solvent and resin component is added to produce a paste having a predetermined viscosity.
  • the present inventor also prepared a paste by dissolving the above-mentioned C1 to C9 or C11 composite silver nanoparticles in toluene.
  • the paste was prepared to have a viscosity that allowed it to flow naturally when tilted at room temperature so that it could be easily applied to a substrate or semiconductor electrode.
  • the paste was stored in a container at room temperature for only 2 weeks. After storage for 2 weeks, a paste film having a thickness of 1 ⁇ m was formed on the circuit board by screen printing, and baked in an electric furnace at 350 ° C. for 20 minutes to form the paste film into a silver film.
  • the surface and cross section of the silver film were observed using an optical microscope and an electron microscope. As a result, some irregularities were found on the surface of the silver film. In the baking at 350 ° C., all organic substances are diffused, but the silver nuclei are not melted, but the surface is melted and the silver nuclei are sintered to form a silver film. Therefore, if the silver nuclei are large, the surface irregularities will be amplified. That is, it was considered that the unevenness on the surface was formed by sintering between large silver nuclei. The reason for the formation of large silver nuclei is considered to be the result of composite silver nanoparticles agglomerating with each other in the paste to form secondary particles during storage for 2 weeks.
  • the composite silver nanoparticles may have aggregated before the addition of the solvent, the composite silver nanoparticles were finely ground in advance in a mortar to be monodispersed, and then the solvent was added to prepare a paste. After leaving this paste for 2 weeks, a paste film was formed on the circuit board and baked at 350 ° C. for 20 minutes. When observed with an electron microscope, the irregularities on the surface of the silver film were somewhat improved, but the irregularities still remained.
  • the composite silver nanoparticles when the composite silver nanoparticles are mixed with a solvent and stored in a fluidized state, the composite silver nanoparticles agglomerate into secondary particles, and the particle size of the secondary particles increases as the storage time increases. The conclusion is reached that increases.
  • the result is that the composite silver nanoparticles are added to a solvent such as toluene having a small viscosity to form a fluid paste having fluidity at room temperature, and the fluid paste is mass-produced and stored for a long period of time. The problem was highlighted.
  • the object of the present invention is to provide a technology for pasting C1-C9 or C11 composite silver nanoparticles in a form that does not aggregate, that is, a non-aggregating paste, and realizing the non-aggregating property with a non-flowable resin. It is to provide a non-flowable paste. Moreover, it is providing the manufacturing method of the non-fluid paste, and also providing the joining method and pattern formation method using a non-fluid paste simultaneously.
  • the present invention has been made in order to solve the above-mentioned problems, and the first embodiment of the present invention has a carbon number of 1 to 9 or around a silver nucleus having an average particle diameter of 1 to 20 nm composed of an aggregate of silver atoms.
  • 11 composed of a metal component containing at least composite silver nanoparticles formed with an organic coating layer composed of at least one alcohol molecule residue, alcohol molecule derivative or alcohol molecule, and the resin is at 10 ° C. or less. It is a composite silver nanopaste that is in a non-flowing state, holds the metal component in a dispersed state, and is fluidized by heating so that it can be applied.
  • the second form of the present invention is a composite silver nanopaste according to the first form, wherein the composite silver nanoparticles are 95 (mass%) or less and the resin is 20 (mass%) or less.
  • a third form of the present invention is a composite silver nanopaste in which silver fine particles having an average particle size of 0.1 to 10 ⁇ m are added as the metal component in the first form.
  • the composite silver nanoparticles are 5 to 85 (mass%), the silver fine particles are 80 to 10 (mass%), and the resin is 20 (mass%).
  • the composite silver nanopaste is as follows.
  • a fifth aspect of the present invention is a composite silver nanopaste according to any one of the first to fourth aspects, wherein a desired amount of a solvent is added to make it flowable even at 10 ° C. or less and can be applied.
  • a resin that is in a non-flowing state at 10 ° C. and fluidized by heating has a carbon number of 1 to 9 or 11 around silver nuclei having an average particle diameter of 1 to 20 nm composed of an aggregate of silver atoms.
  • a composite silver nanoparticle formed with an organic coating layer composed of one or more of alcohol molecule residues, alcohol molecule derivatives or alcohol molecules, and if necessary, silver fine particles are mixed as a metal component, and the resin is fluidized under heating to make the whole Is cooled to a temperature at which the resin becomes non-flowing after kneading, and the metal component is kept in a dispersed state in the resin.
  • a seventh aspect of the present invention is a method for producing a composite silver nanopaste according to the sixth aspect, wherein the silver nuclei have an average particle diameter of 1 to 20 nm and the silver fine particles have an average particle diameter of 0.1 to 10 ⁇ m.
  • An eighth aspect of the present invention is a method for producing a composite silver nanopaste according to the sixth or seventh aspect, wherein a desired amount of solvent is added to make a paste that can be applied by being fluidized even at 10 ° C. or lower. .
  • a composite silver nanopaste of any one of the first to fifth aspects is prepared, a paste layer is formed by applying the composite silver nanopaste to a lower body, and the paste layer is formed on the paste layer.
  • the upper body is placed, the paste layer is silvered by heating, and the lower body and the upper body are joined.
  • a composite silver nanopaste according to any one of the first to fifth aspects is prepared, and the composite silver nanopaste is applied to a predetermined pattern on a surface of a substrate to form a paste pattern.
  • a pattern forming method in which the paste pattern is silvered by heating to form a silver pattern is provided.
  • an alcohol molecule residue, an alcohol molecule derivative or an alcohol molecule having 1 to 9 or 11 carbon atoms is surrounded by a silver nucleus having an average particle diameter of 1 to 20 nm composed of an aggregate of silver atoms. Since composite silver nanoparticles formed with one or more organic coating layers are used, an inexpensive composite silver nanopaste can be provided. Since the composite silver nanoparticles start from inexpensive C1-C9 or C11 alcohol and a relatively inexpensive silver salt (for example, silver carbonate), inexpensive composite silver nanoparticles can be used.
  • the C1 to C9 alcohols are characterized by a relatively small number of carbon atoms and a relatively high silver content in the composite silver nanoparticles compared to the C10 and C12 alcohols.
  • C11 has a carbon number smaller than C12, silver content rate is higher than C12.
  • C1 is methanol
  • C2 is ethanol
  • C3 is propanol
  • C4 is butanol
  • C5 is pentanol
  • C6 is hexanol
  • C7 is heptanol
  • C8 is octanol
  • C9 is nonanol
  • C11 is unidecanol. That is, the composite silver nanoparticle which has the organic coating layer which consists of many Cn alkoxide groups around the silver nucleus which is an aggregate
  • the alcohol residue is a concept including, for example, an alkoxide group C n H 2n + 1 O when the alcohol is written as C n H 2n + 1 OH.
  • the alcohol derivative is a concept including, for example, C n-1 H 2n-1 CHO, C n-1 H 2n-1 COOH, C n-1 H 2n-1 COO, and the like. Alcohol refers to C n H 2n + 1 OH itself.
  • the characteristic of the composite silver nanopaste according to the present invention is the greatest characteristic in the function of the resin.
  • the resin is in a non-flowing state at 10 ° C. or lower, and has a property of holding the composite silver nanoparticles and the silver fine particles in a dispersed state and fluidizing by heating.
  • the non-flowing state means a solid state or a high-viscosity state, and refers to a property of holding the composite silver nanoparticles and the silver fine particles fixedly in a dispersed state.
  • 10 degrees C or less is a temperature range which carries out low temperature storage in a refrigerator, and the said 10 degrees C or less can be achieved by long-term storage by refrigerator storage.
  • the paste when storing in a refrigerator, the paste is in a non-flowing state, and the composite silver nanoparticles and silver fine particles dispersed therein are fixed in the paste by the resin and cannot be aggregated with each other. Therefore, at 10 ° C. or lower, the particles cannot be aggregated with each other, and the particles are completely prevented from aggregating and forming a dump during storage of the paste.
  • This non-flowable paste can be referred to as a non-cohesive paste.
  • the resin when heated to 40 ° C. or higher, the resin is liquefied or the viscosity is suddenly lowered to be in a fluid state, and can be applied to an object as a paste.
  • the paste of the present invention is produced, it is stored at 10 ° C. or less and non-aggregated (non-fluidized). Just before applying the paste to the object, it is heated and fluidized to make a fluid paste, and if this fluid paste is applied to the object, the metal (silver) is not agglomerated so it is extremely dense. A silver film can be formed. If the remaining fluid paste is immediately cooled to 10 ° C. or less, it can be stored for a long time as a non-aggregating paste.
  • Examples of the resin that changes from a high viscosity to a low viscosity by heating include isobornylcyclohexanol (referred to as rosin) and glycerin (referred to as syrup). Since the melting point of glycerin is 17 ° C., solidification is possible if it is set to 10 ° C. or lower in a dry state.
  • As resins that are solid at 10 ° C. or lower and liquefy when heated alcohols such as myristyl alcohol (C14), palmityl alcohol (C16), stearyl alcohol (C18), and behenyl alcohol (C22), and other substances can be used.
  • the resin of the present invention is not a resin having a normal chemical concept, but is a generic term for substances that exhibit non-fluidity at 10 ° C., and is a substance in which everything is diffused by firing and residues such as carbides do not appear. Means.
  • a dispersant is added to disperse the composite silver nanoparticles, or a surfactant is added.
  • a dispersant is added to disperse the composite silver nanoparticles, or a surfactant is added.
  • these impurity organic substances are added, not only the silver content is lowered, but also when fired, A large amount of gas is generated from the impurity organic substance, and a large amount of voids (bubble voids) are formed in the silver film by this gas.
  • the electrical conductivity is lowered and the bonding force with the substrate is lowered. Bonding performance is reduced.
  • the silver content can be kept high, and at the same time, the amount of generated gas is small, the number of voids is inevitably reduced, the increase in bonding force and electrical conductivity and There is an effect that the thermal conductivity can be increased.
  • a composite silver nanopaste in which the composite silver nanoparticles are 95 (mass%) or less and the resin is 20 (mass%) or less.
  • the simplest paste composition is a mixture of composite silver nanoparticles and resin.
  • the silver component is only composite silver nanoparticles
  • the maximum mass% is 95 mass%
  • the minimum mass% of the resin is 5 mass%. What is necessary is just to increase the mass% of resin according to the fall of the mass% of a composite silver nanoparticle.
  • the silver content in the paste is preferably 80 mass% or more, the mass% of the resin is preferably set to 20 mass% or less.
  • a composite silver nanopaste to which silver fine particles having an average particle size of 0.1 to 10 ⁇ m are added as the metal component.
  • silver fine particles are added as the silver component in addition to the composite silver nanoparticles. Since the silver fine particles are pure silver and do not contain any organic matter, the silver content in the paste can be increased by adding silver fine particles. Since the particle diameter of the silver fine particles is 0.1 to 10 ⁇ m and the silver nucleus particle diameter of the composite silver nanoparticles is 1 to 20 nm, the composite silver nanoparticles are considered to play a role of an adhesive between the silver fine particles. It is done.
  • the composite silver nanoparticles adhere to the surface of the silver fine particles, the organic components are diffused by firing, and the silver fine particles whose surfaces are melted are bonded to each other.
  • the composite silver nanoparticles accumulate in the gaps between the large silver fine particles and the organic matter is diffused by firing, the gaps between the silver fine particles are filled with silver nuclei, and the silver fine particles are Therefore, the silver film itself is densely formed, and a conductor having high strength and high electrical conductivity is provided.
  • the silver nuclei fill the gaps between the silver fine particles, and the gas nuclei are filled back into the voids (voids) after the gas is diffused, and the number of voids is reduced. As a result, it is possible to improve the bonding strength and electrical conductivity with the substrate.
  • the composite silver nanoparticles are 5 to 85 (mass%), the silver fine particles are 80 to 10 (mass%), and the resin is 20 (mass%) or less.
  • a silver nanopaste is provided.
  • the composition of the composite silver nanopaste is composite silver nanoparticles, silver fine particles, and a resin.
  • the composite silver nanoparticles are 5 to 85 (mass%). When the composite silver nanoparticles are less than 5 mass%, the adhesion performance between the silver fine particles is deteriorated.
  • the organic content in the paste becomes excessive. Further, the silver fine particles are 80 to 10 (mass%).
  • the mass is 80 mass% or more, the content of the composite silver nanoparticles is lowered, the adhesion between the silver fine particles is lowered, and when the mass is 10 mass% or less, There is a weak point that the silver content of is reduced. Therefore, within the above range, preparing a composite silver nanopaste having an appropriate silver content, efficiently diffused during firing, and restricting the amount of voids (bubble removal) to an appropriate value Can do.
  • a composite silver nanopaste that can be applied by adding a desired amount of a solvent to make it flowable even at 10 ° C. or lower.
  • a paste to which only a resin is added is provided, and even if the paste is stored at a temperature of 10 ° C. or lower for a long period of time, the paste does not have fluidity. Are immobilized and mutual aggregation does not occur.
  • the solvent of the fifth embodiment can be added and fluidized, and the flowable paste can be applied to the substrate by a dispenser.
  • the non-fluid paste there are two methods: heating and adding a solvent.
  • a solvent since the organic substance content in the paste increases, there is a weak point in which the amount of gas generated by firing increases and the amount of void generation increases.
  • the solvent has a function of reducing the viscosity of the paste, and general organic solvents that evaporate at a relatively low temperature can be used. For example, C1-C8 alcohol, xylene, toluene, acetone, hexane, and other solvents can be used.
  • a resin that is in a non-flowing state at 10 ° C. and fluidized by heating has a carbon number of 1 to 9 around silver nuclei having an average particle diameter of 1 to 20 nm composed of an aggregate of silver atoms.
  • the resin is in a non-flowing state at 10 ° C. and has a characteristic of being fluidized by heating.
  • heating is not only heating by a heating means, but also friction during kneading releases frictional heat, so friction is included in one form of heating.
  • friction is included in one form of heating.
  • a two-stage kneading in which a composite silver nanoparticle is added and kneaded after kneading a resin and silver fine particles.
  • silver fine particles are not added, there is only a form of kneading the resin and composite silver nanoparticles.
  • the paste fluidized by heat kneading is cooled to be non-fluidized and stored as a non-fluidized paste. Therefore, in non-fluid storage, composite silver nanoparticles and silver fine particles are not aggregated in the paste.
  • the seventh aspect of the present invention there is provided a method for producing a composite silver nanopaste in which the average particle diameter of the silver nuclei is 1 to 20 nm and the average particle diameter of the silver fine particles is 0.1 to 10 ⁇ m.
  • the silver content in the paste can be increased. Since the particle diameter of the silver fine particles is 0.1 to 10 ⁇ m and the silver core particle diameter of the composite silver nanoparticles is 1 to 20 nm, when the paste is fired, the composite silver nanoparticles are between the silver fine particles. It is thought to play the role of an adhesive.
  • the composite silver nanoparticles adhere to the surface of the silver fine particles, the organic components are diffused by firing, and the silver fine particles whose surfaces are melted are bonded to each other.
  • the composite silver nanoparticles accumulate in the gaps between the large silver fine particles, and when the organic matter is diffused by firing, the gaps between the silver fine particles are filled with silver nuclei, Since the silver fine particles are bonded to each other by the silver nuclei, the silver film itself is densely formed, and a silver conductor having high strength and high electrical conductivity is provided.
  • the silver nuclei fill the gaps between the silver fine particles, and the gas nuclei are filled back into the bubble cavities (voids), and the number of voids is reduced. As a result, it is possible to improve the bonding strength and electrical conductivity with the substrate.
  • a method for producing a composite silver nanopaste that is made into a paste that can be applied by adding a desired amount of solvent to make it flowable even at 10 ° C. or lower.
  • the composite silver nanopaste of the present invention is in a non-flowing state at a low temperature.
  • a method for producing a paste that is in a fluid state even at 10 ° C. is provided by adding a solvent to the production method of the sixth embodiment or the seventh embodiment.
  • the solvent has a function of reducing the viscosity of the paste, and general organic solvents that evaporate at a relatively low temperature can be used.
  • organic solvents that evaporate at a relatively low temperature
  • C1-C8 alcohol, xylene, toluene, acetone, hexane, and other solvents can be used.
  • alcohol is advantageous as a solvent.
  • the composite silver nanopaste of the present invention is prepared, the composite silver nanopaste is applied to the lower body to form a paste layer, and the upper body is disposed on the paste layer,
  • a joining method in which the paste layer is silvered by heating to join the lower body and the upper body.
  • This embodiment is a method for joining two objects using the composite silver nanopaste according to the present invention, in which one object is referred to as a lower body and the other object is referred to as an upper body, and both are bonded via a paste layer and fired.
  • strong bonding can be achieved by silvering the paste layer.
  • the silver film is excellent in electrical conductivity and thermal conductivity and can be fired at a low temperature, it is possible to join low melting point objects.
  • the composite silver nanopaste of the present invention is prepared, the composite silver nanopaste is coated on the surface of the substrate in a predetermined pattern, and the paste pattern is formed by heating.
  • a pattern forming method is provided in which a silver pattern is formed by silveration. For example, when a silver film having a predetermined pattern is formed on a resin substrate having a low melting point, a method for forming a silver film having various patterns on various materials at a low temperature is provided according to the embodiment of the present invention.
  • FIG. 1 is a production process diagram of composite silver nanoparticles CnAgAL.
  • FIG. 2 is a first process diagram of a formation reaction of composite silver nanoparticles.
  • FIG. 3 is a second process diagram of the formation reaction of composite silver nanoparticles.
  • FIG. 4 is a high-resolution transmission electron microscope view of C2AgAL.
  • FIG. 5 is a high-resolution transmission electron microscope view of C4AgAL.
  • FIG. 6 is a thermal analysis diagram of C2AgAL.
  • FIG. 7 is a thermal analysis diagram of C4AgAL.
  • FIG. 8 is a production process diagram of a composite silver nanopaste.
  • FIG. 9 is a characteristic diagram of the viscosity and temperature of IBCH.
  • FIG. 9 is a characteristic diagram of the viscosity and temperature of IBCH.
  • FIG. 10 is a thermal analysis diagram of IBCH with a heating rate of 3 ° C./min.
  • FIG. 11 is a graph showing the relationship between the evaporation temperature of IBCH and the temperature rise rate.
  • FIG. 12 is a characteristic diagram of viscosity and temperature of glycerin.
  • FIG. 13 is a thermal analysis diagram of the composite silver nanopaste (C2AgAL) in the atmosphere.
  • FIG. 14 is a thermal analysis diagram of the composite silver nanopaste (C4AgAL) in the atmosphere.
  • FIG. 15 is a thermal analysis diagram of the composite silver nanopaste (C6AgAL) in the atmosphere.
  • Table 1 is a list of molar ratios of the raw materials for production of the composite silver nanoparticles used in the present invention and the alcohol solution.
  • An inorganic silver salt or an organic silver salt can be used as the silver raw material, and silver carbonate (Ag2CO3) is described as an example of the inorganic silver salt.
  • the number of moles of alcohol in which 100 g (0.363 moles) of silver carbonate fine particles are dispersed ranges from 3.63 moles to 23.2 moles (mole ratio of alcohol / moles of silver carbonate). Number) is in the range of 10-63.9.
  • the composite silver nanoparticles CnAgAL produced by chemical reaction have a very small silver core particle size of 1 to 20 nm, preventing collisions between the composite silver nanoparticles in an alcohol solution, and forming secondary particles by aggregation. It is for suppressing. Ten types of composite silver nanoparticles are produced.
  • Table 2 is a list of molecular weights of raw materials for composite silver nanoparticles and the number of moles of 100 g.
  • Specific names of alcohol (C n H 2n + 1 OH) are methanol (CH 3 OH), ethanol (C 2 H 5 OH), propanol (C 3 H 7 OH), butanol (C 4 H 9 OH), pen ethanol (C 5 H 11 OH), hexanol (C 6 H 13 OH), heptanol (C 7 H 15 OH), octanol (C 8 H 17 OH), nonanol (C 9 H 19 OH), Unidekanoru (C 10 H 21 OH).
  • the boiling point BT (° C.) of the alcohol is also shown.
  • FIG. 1 is a production process diagram of composite silver nanoparticles.
  • a mixed solution of a predetermined amount of silver salt powder and a predetermined amount of alcohol is prepared, and the mixed solution is sealed in a reaction vessel.
  • the mixed solution is heated at a generation temperature PT (° C.) for a predetermined time under an Ar gas flow.
  • PT generation temperature
  • the reaction time is preferably within 1 hour.
  • the composite silver nanoparticles start to aggregate with each other and become secondary particles. Therefore, it is desirable to cool rapidly after the reaction.
  • the composite silver nanoparticles are recovered from the reaction solution as a powder.
  • the composite silver nanoparticle is expressed as CnAgAL, which indicates that it is an alkoxide type composite silver nanoparticle.
  • FIG. 2 is a first process diagram of a formation reaction of composite silver nanoparticles according to the present invention.
  • R n in the formula (3) represents a hydrocarbon group C n H 2n + 1 of the alcohol.
  • the carbon number n is limited to 10 of 1 to 9 or 11.
  • Many silver salt fine particles are insoluble in alcohol, and the hydrophilic group OH of alcohol has a property of easily bonding to the surface of the silver salt fine particles.
  • the hydrophobic group R n of the alcohol has a high affinity with alcohol solvent.
  • Equation (4) silver carbonate (Ag 2 CO 3) is shown as a silver salt.
  • FIG. 3 is a second process diagram of a formation reaction of composite silver nanoparticles according to the present invention.
  • silver carbonate is used as a silver salt.
  • Silver carbonate on the surface of the silver carbonate fine particles reacts with alcohol to form aldehyde R n-1 CHO simultaneously with silveration, as shown in formula (5).
  • aldehyde has a strong reducing action, and as shown in formula (7), silver carbonate is reduced to form carboxylic acid R n-1 COOH simultaneously with silveration.
  • FIG. 4 is a high-resolution transmission electron microscope diagram of C2AgAL.
  • the composite silver nanoparticles C2AgAL were produced in a monodispersed state at a production temperature PT of 65 ° C., and photographed with a high resolution transmission electron microscope.
  • Lattice images consisting of parallel lines were observed in the silver nuclei, confirming that the silver nuclei were single crystals.
  • the lattice spacing of the lattice image is 0.24 nm, which matches the (111) plane spacing of the bulk silver crystal, confirming that the silver nucleus is a silver single crystal.
  • FIG. 5 is a high resolution transmission electron microscope diagram of C4AgAL.
  • the composite silver nanoparticle C4AgAL was produced in a monodispersed state at a production temperature PT of 80 ° C., and was photographed with a high resolution transmission electron microscope.
  • Lattice images consisting of parallel lines were observed in the silver nuclei, confirming that the silver nuclei were single crystals.
  • the lattice spacing of the lattice image was 0.24 nm, which coincided with the (111) plane spacing of the bulk silver crystal, and it was confirmed that the silver nucleus was a silver single crystal.
  • the organic coating layer is strongly decomposed and diffused at the DTA peak temperature T2, and the temperature at which the diffusion is completed corresponds to the metallization temperature T3.
  • TG curve thermogravimetric measurement curve
  • T1 ⁇ T2 ⁇ T3 is generally established, and it has become clear from the numerous experiments conducted by the present inventors that there is a relationship of T2-60 ⁇ T1 ⁇ T2. In other words, it was found that the TG decrease start temperature T1 is within 60 ° C. below the DTA peak temperature T2, and at the same time, is not more than the DTA peak temperature T2.
  • the DTA curve is a differential thermal analysis curve
  • the TG curve is a thermogravimetric curve.
  • TG decrease start temperature T1 103 ° C.
  • DTA peak temperature T2 120 ° C.
  • metallization temperature (silvering temperature) T3 122 ° C. It is also clear that the relationship of T2-60 ⁇ T1 ⁇ T2 is established.
  • the generation temperatures PT of the 10 types of composite silver nanoparticles CnAgAL were all 100 ° C. or lower, and as a result, the DTA peak temperature T2 was also suppressed to 150 ° C. or lower.
  • the metallization temperature T3 is slightly higher than the DTA peak temperature T2, it was shown that the metallization temperature T3 is also 150 ° C. or less.
  • CnAgAL is produced by keeping an alcohol solution at a constant production temperature PT, and since the boiling point of the alcohol is constant in the atmosphere, the production temperature PT can be easily kept at the boiling point BT by reacting the alcohol in a boiling state. . Since the alcohol boiling point of C1 to C3 is 100 ° C. or less, it means that three types of CnAgAL with 1 ⁇ n ⁇ 3 can be produced by alcohol boiling reaction. Of course, other temperature control methods can be used.
  • Table 4 shows the range of the TG decrease start temperature T1 of the composite silver nanoparticles CnAgAL. Table 4 shows the temperatures of T2-60, T1 and T2 with respect to C1 to C9 and C11. As a result, it was found that T2-60 ⁇ T1 ⁇ T2 holds for 10 types of composite silver nanoparticles.
  • FIG. 8 is a production process diagram of composite silver nanopaste.
  • a predetermined weight percent of composite silver nanoparticle CnAgAL powder, a predetermined weight percent of silver fine particle Ag powder, and a predetermined weight percent of resin are prepared, and these three components are put into a mixing container.
  • the resin is fluidized by heating to 40 ° C. in a mixing container, and the paste is uniformly mixed.
  • a rotation-revolution centrifuge that performs rotation at 700 rpm and revolution at 2000 rpm was used. If the heating temperature is about 40 ° C., the temperature is naturally raised by frictional heat, and therefore a forced heating operation is unnecessary. However, when it is 40 ° C. or higher, it can be efficiently fluidized by heating with a heater. Thereafter, the composite silver nanopaste is rapidly cooled, solidified and recovered. By solidification, the uniformly dispersed composite silver nanoparticles and silver fine particles are fixed by the resin and do not aggregate during storage.
  • a method in which the manufacturing process of FIG. 8 is modified is also adopted.
  • a paste intermediate is produced by mixing a predetermined weight% of composite silver nanoparticles CnAgAL powder and a predetermined weight% of resin while heating.
  • a predetermined weight percent of silver fine particle Ag powder is uniformly mixed with this paste intermediate while heating to produce a composite silver nanopaste, which is rapidly cooled to solidify.
  • frictional heat is used, forced heating is not necessary.
  • the composite silver nanoparticles are uniformly dispersed in the resin, and then the silver fine particles are uniformly dispersed. Therefore, the composite silver nanoparticles and the silver fine particles are dispersed independently, and uniform to eliminate the interaction between the two. It is characterized by further increasing dispersibility.
  • a paste intermediate is produced by mixing a predetermined weight% of silver fine particle Ag powder and a predetermined weight% of resin while heating.
  • a predetermined weight percent of composite silver nanoparticle CnAgAL powder is uniformly mixed with this paste intermediate while heating to produce a composite silver nanopaste, which is rapidly cooled to solidify.
  • frictional heat is used, forced heating is not necessary.
  • the silver fine particles are first uniformly dispersed in the resin, and then the composite silver nanoparticles are uniformly dispersed. Therefore, the composite silver nanoparticles and the silver fine particles are independently dispersed to eliminate the interaction between the two. Uniform dispersibility is further increased. Of course, when silver fine particles are not added, it is needless to say that only uniform mixing of CnAgAL and resin is sufficient.
  • IBCH Isobornylcyclohexanol
  • ICBH cyclohexanol
  • Table 5 is an exemplary table of resins used in the present invention.
  • IBCH is a so-called rosin-like, has no fluidity at room temperature, and has a property of fluidizing rapidly by heating.
  • Glycerin has a lower viscosity than ICBH and is in the form of a so-called syrup, but has a melting point of 17 ° C., and thus solidifies at 10 ° C. in an environment without moisture. Therefore, glycerin almost loses its fluidity when cooled to the refrigerator temperature or lower, and fluidizes when heated, so that it can be used as the resin of the present invention in the same manner as IBCH.
  • Both ICBH and glycerin are decomposed and diffused by firing in the air, and no carbides remain.
  • a substance that is solid at room temperature of 10 ° C. or less, has a property of being liquefied when it is 40 ° C. or more, and completely disperses when baked can be used as the resin of the present invention.
  • higher alcohols having 14 or more carbon atoms can be used, and myristyl alcohol, palmityl alcohol, stearyl alcohol, behenyl alcohol and the like are listed. Their melting points are as shown in Table 3. Needless to say, resins similar to those described above can also be used as the resin of the present invention.
  • Table 6 is a relationship table between viscosity and temperature of IBCH. Since it is 150,000 centipoise (cP) at 30 ° C or lower, naturally it does not have fluidity even at 10 ° C, but when it reaches 40 ° C or higher, especially 50 ° C or higher, fluidity is rapidly developed and is optimal for the present invention Resin.
  • cP centipoise
  • FIG. 9 is a characteristic diagram of viscosity and temperature of IBCH.
  • the relationship between the viscosity and the temperature shown in Table 6 is plotted, and it can be seen that IBCH has a property of changing with temperature so rapidly that the viscosity is displayed on the logarithmic axis. All resins having such properties and having the property of being completely diffused by firing can be used in the present invention.
  • FIG. 10 is a thermal analysis diagram of IBCH with a temperature increase rate of 3 ° C./min. From DTA, the complete evaporation temperature is 205 ° C., and from TG, the weight is found to be 0% at 205 ° C., and it is proved that the entire amount has evaporated and disappeared.
  • Table 7 is a relationship table between the temperature increase rate of IBCH and the evaporation temperature.
  • a temperature increase rate of 3 (° C./min) means a program temperature increase in which the temperature is increased while increasing by 3 ° C. per minute.
  • the evaporation temperature decreases as the temperature increase rate decreases, and the evaporation temperature increases as the temperature increase rate increases. This property can be said to be a property of TG / DTA measurement.
  • FIG. 11 is a graph showing the relationship between the evaporation temperature of IBCH and the temperature rise rate. The relationship between the evaporation temperature shown in Table 7 and the temperature rising rate is plotted. Based on this graph, the evaporation rate can be arbitrarily adjusted by adjusting the temperature increase rate.
  • Table 8 is a relationship table between glycerin viscosity and temperature. At 0 ° C., it is 12100 centipoise (cP). Upon further cooling, the viscosity increases rapidly and becomes non-flowing. On the other hand, when the temperature is set to 10 ° C. or higher, the viscosity becomes 3900 (cP) or lower and exhibits fluidity. At this level of viscosity, the non-flowability may be considered to be small, but these viscosities are open to the atmosphere and absorb moisture. In particular, the melting point of glycerin is 17 ° C., and in an environment without moisture, it becomes solid when it becomes 17 ° C. or lower.
  • non-fluidity at 10 ° C. or lower. While IBCH exhibits a slightly high temperature resin characteristic, glycerin is a resin that exhibits a low temperature resin characteristic, and by appropriately using both, non-fluidity / fluidity change can be realized. As described above, non-fluidity means non-aggregation of composite silver nanoparticles.
  • FIG. 12 is a characteristic diagram of viscosity and temperature of glycerin.
  • the relationship between the viscosity and the temperature shown in Table 8 is plotted, and it can be seen that the glycerin resin also has a property of rapidly changing with respect to temperature as the viscosity is displayed on the logarithmic axis. All resins having such properties and having the property of being completely diffused by firing can be used in the present invention.
  • Table 9 is a list of alcohols used as solvents.
  • the composite silver nanoparticles have the property of dissolving very well in alcohol.
  • the alcohol methanol, ethanol, butanol, hexanol, and octanol can be used.
  • organic solvents such as acetone, ether, benzene, ethyl acetate, terpineol, dihydroterpineol, butyl carbitol, cellosolve and the like can be used.
  • the addition of a solvent reduces the silver content and causes agglomeration of composite silver nanoparticles and silver fine particles when it is made into a fluid paste, so a non-fluid paste without a solvent during storage and storage. It is recommended to add a solvent just before coating. Even when the storage period is very short, there is a possibility of aggregation, and therefore the addition of a solvent immediately before coating is desired. Even when a solvent is added, the amount added is preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 1 to 2% by mass.
  • Example 11 to 113 Three types of composite silver nanopastes of C1 to C9 and C11]
  • a composite silver nanopaste was prepared using the composite silver nanoparticles.
  • the following three types of pastes were prepared from C1 to C9 and C11 CnAgAL, respectively.
  • One of the three types of CnAgAL was CnAgAL having a metallization temperature T3 shown in Table 3, and the other two were CnAgALs having another slightly different metallization temperature T3.
  • CnAgAL having a metallization temperature T3 above 150 ° C. is also used.
  • the solvent was selected from methanol, ethanol, butanol, xylene, and toluene.
  • the resin was selected from IBCH, glycerin, myristyl alcohol (C 14 H 29 OH), palmityl alcohol (C 16 H 33 OH), stearyl alcohol (C 18 H 37 OH).
  • the particle size of the silver particles, the type of solvent, the type of resin, the mass% of each component, and the paste baking temperature in the atmosphere are as described in Tables 10 and 11.
  • the resin is first heated to 50 ° C. and fluidized, CnAgAL powder is mixed and kneaded in this, and cooled to 10 ° C. or lower after kneading.
  • a non-flowable paste was prepared.
  • this non-flowable paste is heated to 50 ° C. to be fluidized and applied to the test surface.
  • the atmospheric paste firing temperature T is set higher than the metallization temperature T3 of CnAgAL. This is because it is necessary not only to metallize CnAgAL but also to evaporate the solvent and evaporate or decompose the resin. In addition, if the CnAgAL paste is baked at a temperature higher than the metallization temperature T3, an excellent metal film can be formed and a silver film having high electrical conductivity can be formed. The excellence of the silver film increases as the firing temperature T in the atmosphere increases. Therefore, as shown in Tables 10 and 11, the atmospheric paste firing temperature T was set higher than the metallization temperature T3.
  • FIG. 13 is a thermal analysis diagram of the C2AgAL paste of Example 23.
  • peaks up to 150 ° C. indicate that IBCH has evaporated.
  • the step up to 175 ° C. shows the decomposition and diffusion of the organic coating layer of C2AgAL. This fact is also understood from the fact that the TG step and the DTA peak coincide.
  • FIG. 14 is a thermal analysis diagram of the C4AgAL paste of Example 43.
  • peaks up to 150 ° C. indicate that IBCH has evaporated.
  • the step up to 175 ° C. shows the decomposition and diffusion of the organic coating layer of C4AgAL. This fact is also understood from the fact that the TG step and the DTA peak coincide.
  • FIG. 15 is a thermal analysis diagram of the C6AgAL paste of Example 63.
  • peaks up to 150 ° C. indicate that IBCH has evaporated.
  • the step up to 195 ° C. shows the decomposition and diffusion of the organic coating layer of C6AgAL. This fact can be understood from the fact that the TG step and the DTA peak coincide.
  • Example 114 Joining of semiconductor electrode and circuit board
  • a bonding test was performed with the semiconductor chip as the upper body and the circuit board as the lower body.
  • the electrode end of the semiconductor chip was inserted into the through hole of the circuit board, and the composite silver nanopaste of Example 11 to Example 113 was applied to the contact part between them to obtain 30 types of paste specimens.
  • the said coating part was heated locally with the paste baking temperature T of Table 10 and Table 11, the said coating part was metalized, and joining was completed. After cooling, when the appearance of the joint was inspected with an optical microscope, there were no problems with 30 types of specimens. An electrical continuity test and an electrical resistance measurement were performed, and it was confirmed that it functions effectively as an alternative solder. From the 30 types of bonding tests, it was found that the composite silver nanopaste according to the present invention can be used industrially as an alternative solder.
  • Example 115 Formation of silver pattern on heat-resistant glass substrate
  • the composite silver nanopastes of Examples 11 to 113 were screen-printed on the base to obtain 30 types of test bodies on which a predetermined paste pattern was formed.
  • the said test body was heated with the atmospheric paste baking temperature T of Table 10 and Table 11 with the electric furnace, and the silver pattern was formed from the said paste pattern.
  • T of Table 10 and Table 11 with the electric furnace
  • the silver pattern was formed from the said paste pattern.
  • After cooling when the surface of the silver pattern was inspected with an optical microscope, there were no problems with 30 types of specimens. From the 30 types of pattern formation tests, it was found that the composite silver nanopaste according to the present invention can be used industrially as a silver pattern forming material.
  • a silver nucleus having an average particle diameter of 1 to 20 nm composed of an aggregate of silver atoms is composed of one or more alcohol molecule residues, alcohol molecule derivatives or alcohol molecules having 1 to 9 or 11 carbon atoms.
  • a metallic component containing at least composite silver nanoparticles having an organic coating layer is mixed with a resin. The resin is in a non-flowing state at 10 ° C. or lower, and the metallic component is held in a dispersed state.
  • a composite silver nanopaste that can be fluidized and applied is provided.
  • a paste that prevents aggregation of composite silver nanoparticles by non-fluidity and develops coating performance by heat fluidity is provided.
  • the composite silver nanopaste of the present invention can be used for electronic materials such as alternative solder, printed wiring, and conductive materials, magnetic materials such as magnetic recording media, electromagnetic wave absorbers, and electromagnetic resonators, far-infrared materials, and composite film forming materials. It can be applied to pastes in various fields such as structural materials, ceramics / metal materials such as sintering aids / coating materials, and medical materials.

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Abstract

L'invention concerne une technique de conversion en pâte de nanoparticules d'argent composites C1-9 ou C11 utilisant une résine qui n'est pas fluide à une température inférieure ou égale à 10 °C de façon à empêcher l'agglomération des nanoparticules lors du stockage, et concerne donc une pâte non fluide de telles nanoparticules. L’invention concerne une pâte de nanoparticules d'argent composites préparée par mélange avec une résine d'un composant métallique contenant essentiellement des nanoparticules d'argent composites constituées d'un noyau d'argent, formé d'agrégats d'atomes d'argent, d'un diamètre compris entre 1 et 20 nm, et d'une couche organique recouvrant le noyau, composée d'au moins un élément parmi les composants suivants, à savoir des résidus d'alcool, des dérivés d'une molécule d'alcool et des molécules d'alcool, chacun de ces composants contenant de 1 à 9, voire 11 atomes de carbone. L’invention est caractérisée en ce que, à une température inférieure ou égale à 10 °C, la résine est dans un état non fluide pour maintenir le composant métallique dans un état dispersé, mais elle peut être fluidifiée par chauffage pour permettre son application.
PCT/JP2008/062238 2008-01-17 2008-07-04 Pâte de nanoparticules d'argent composites, son procédé de production, procédé de connexion et procédé de formation de motifs WO2009116185A1 (fr)

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JP2010503736A JP5306322B2 (ja) 2008-03-18 2008-07-04 複合銀ナノペースト、その製法、接合方法及びパターン形成方法
CN2008801281306A CN101990474B (zh) 2008-01-17 2008-12-25 复合银纳米粒子、复合银纳米糊膏、其制法、制造装置、接合方法及图案形成方法
US12/735,435 US8348134B2 (en) 2008-01-17 2008-12-25 Composite silver nanoparticle, composite silver nanopaste, bonding method and patterning method
PCT/JP2008/073660 WO2009090846A1 (fr) 2008-01-17 2008-12-25 Nanoparticules d'argent composites, nanopâte d'argent composite, et leurs procédé de production, appareil de production, procédé de conjugaison et procédé de modelage
KR1020107017975A KR101222304B1 (ko) 2008-01-17 2008-12-25 복합 은나노입자, 복합 은나노 페이스트, 그 제법, 제조장치, 접합방법 및 패턴 형성방법
EP08870788.0A EP2298471B1 (fr) 2008-01-17 2008-12-25 Nanoparticules d'argent composites, nanopâte d'argent composite, et leurs procédé de production
JP2009549977A JP4680313B2 (ja) 2008-01-17 2008-12-25 複合銀ナノ粒子、複合銀ナノペースト、その製法、製造装置、接合方法及びパターン形成方法
PCT/JP2008/073751 WO2009090849A1 (fr) 2008-01-17 2008-12-26 Procédé de microcâblage et structure comprenant une partie électronique montée
US13/707,298 US8459529B2 (en) 2008-01-17 2012-12-06 Production method of composite silver nanoparticle
US13/707,384 US8906317B2 (en) 2008-01-17 2012-12-06 Production apparatus of composite silver nanoparticle

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JP2016000861A (ja) * 2010-11-22 2016-01-07 Ｄｏｗａエレクトロニクス株式会社 接合材料および接合体
JP2017101264A (ja) * 2015-11-30 2017-06-08 Ｄｏｗａエレクトロニクス株式会社 接合材およびそれを用いた接合方法
JP2018206840A (ja) * 2017-05-31 2018-12-27 株式会社応用ナノ粒子研究所 放熱構造体

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FR2953679B1 (fr) * 2009-12-04 2012-06-01 Thales Sa Boitier electronique hermetique et procede d'assemblage hermetique d'un boitier
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JP2013079431A (ja) * 2011-10-05 2013-05-02 Nippon Synthetic Chem Ind Co Ltd:The 金属複合超微粒子の製造方法
JP2013079430A (ja) * 2011-10-05 2013-05-02 Nippon Synthetic Chem Ind Co Ltd:The 金属複合超微粒子の製造方法
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JP6373066B2 (ja) 2014-05-30 2018-08-15 Ｄｏｗａエレクトロニクス株式会社 接合材およびそれを用いた接合方法
CN111095441B (zh) 2017-09-20 2021-11-23 积水化学工业株式会社 含金属粒子、连接材料、连接结构体及连接结构体的制造方法、导通检查用部件以及导通检查装置

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JP2017101264A (ja) * 2015-11-30 2017-06-08 Ｄｏｗａエレクトロニクス株式会社 接合材およびそれを用いた接合方法
JP2018206840A (ja) * 2017-05-31 2018-12-27 株式会社応用ナノ粒子研究所 放熱構造体

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