WO2015129562A1 - 低温焼結性に優れる銀ペースト及び該銀ペーストの製造方法 - Google Patents

低温焼結性に優れる銀ペースト及び該銀ペーストの製造方法 Download PDF

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WO2015129562A1
WO2015129562A1 PCT/JP2015/054723 JP2015054723W WO2015129562A1 WO 2015129562 A1 WO2015129562 A1 WO 2015129562A1 JP 2015054723 W JP2015054723 W JP 2015054723W WO 2015129562 A1 WO2015129562 A1 WO 2015129562A1
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silver
metal paste
silver particles
particles
solid content
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PCT/JP2015/054723
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English (en)
French (fr)
Japanese (ja)
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勇一 牧田
久保　仁志
優輔 大嶋
淳一 谷内
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田中貴金属工業株式会社
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Application filed by 田中貴金属工業株式会社 filed Critical 田中貴金属工業株式会社
Priority to DE112015000957.4T priority Critical patent/DE112015000957B4/de
Priority to CN201580010191.2A priority patent/CN106062886B/zh
Priority to KR1020187009140A priority patent/KR20180036799A/ko
Priority to KR1020167023468A priority patent/KR101866111B1/ko
Publication of WO2015129562A1 publication Critical patent/WO2015129562A1/ja

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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
    • H01B1/20—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
    • 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
    • B22F1/056—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
    • B22F1/07—Metallic powder characterised by particles having a nanoscale microstructure
    • 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
    • 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
    • B22F1/107—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material containing organic material comprising solvents, e.g. for slip casting
    • 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
    • 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
    • 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
    • B22F2301/00—Metallic composition of the powder or its coating
    • B22F2301/25—Noble metals, i.e. Ag Au, Ir, Os, Pd, Pt, Rh, Ru
    • B22F2301/255—Silver or gold

Definitions

  • the present invention relates to a metal paste in which silver particles are dispersed in a solvent.
  • a metal paste essentially containing silver particles having a particle size of 100 to 200 nm, which can be sintered at a relatively low temperature of 150 ° C. or lower and can produce a low-resistance silver sintered body.
  • paste a metal paste essentially containing silver particles having a particle size of 100 to 200 nm, which can be sintered at a relatively low temperature of 150 ° C. or lower and can produce a low-resistance silver sintered body.
  • a metal paste in which conductive metal particles are kneaded and dispersed in a solvent as a solid content is used as a circuit forming material in printed electronics and as a conductive bonding material for bonding various semiconductor elements to a substrate.
  • This metal paste is applied to a substrate or a member to be joined and then heated and fired to sinter the metal particles, thereby forming circuits / electrodes, joints / bonding portions.
  • a metal paste that applies silver particles as metal particles is attracting attention as a particularly useful metal paste for the above applications.
  • Silver is a metal having a low specific resistance, and an appropriately formed sintered body can effectively act as a conductive film.
  • silver has the advantage of excellent thermal conductivity, and the metal paste to which silver is applied can be used as a bonding material and heat conduction material for manufacturing semiconductor devices in which the operating temperature is increased due to the large current of power devices and the like. It is supposed to be effective.
  • Patent Document 1 includes silver nanoparticles having an average primary particle diameter of 1 to 200 nm and a dispersion medium having a boiling point of 230 ° C. or more, and further 0.5 to 3.0 ⁇ m.
  • a bonding material comprising submicron silver particles of the following is described.
  • the bonding material made of the metal paste described in Patent Document 1 has a bonding temperature (sintering temperature) for silver particle sintering of 200 ° C. or higher. This bonding temperature can be said to be lower than that of the brazing material, but it is difficult to say that the bonding temperature is sufficiently low.
  • the level of the joining temperature is an element that can affect the semiconductor element that is the material to be joined, and it is desirable that the joining temperature be as low as possible.
  • the sintering temperature of metal particles the possibility of adjustment by controlling the size (particle size) is known.
  • This is referred to as a so-called nano-size effect, and is a phenomenon in which the melting point of the metal particles is remarkably lowered as compared with the bulk material when the nano-particles are tens of nanometers or less.
  • the metal paste described in Patent Document 1 contains silver particles with a relatively large particle size of submicron size, so it is considered difficult to sinter at low temperatures. However, if this nanosize effect is used, sintering is performed at a lower temperature. It is believed that a possible metal paste can be obtained.
  • nano-level silver particles those produced by a thermal decomposition method of a silver complex according to Patent Document 2 have been reported.
  • a heat-decomposable silver compound such as silver oxalate (Ag 2 C 2 0 4 ) is used as a raw material to react with an appropriate organic substance to form a precursor complex, which is heated to form silver particles. How to get.
  • minute nano-level silver particles having an average particle diameter of a few nanometers to a few tens of nanometers with relatively uniform particle diameters can be produced.
  • the metal paste composed of the nano-level silver particles Although nano-level silver particles are sintered at a low temperature of 200 ° C. or lower, the resistance value of the sintered body tends to be considerably higher than that of the bulk material. This problem greatly impairs the usefulness of the metal paste as a circuit material or a conductive bonding material.
  • the present invention can sinter silver particles in a low temperature range for a metal paste containing silver particles, and can form a sintered body with low resistance and a sintered body with excellent thermal conductivity. Offer things.
  • a low temperature range of 150 ° C. or lower was set as the target value of the sintering temperature.
  • the present invention for solving the above-mentioned problems is a metal paste obtained by kneading a solid content composed of silver particles and a solvent, wherein the solid content contains 30% or more of silver particles having a particle size of 100 to 200 nm on the basis of the number of particles. Further, the silver particles constituting the solid content are a metal paste in which an amine compound having a total carbon number of 4 to 8 is bonded as a protective agent.
  • the metal paste according to the present invention contains a certain proportion or more of silver particles constituting a solid content kneaded with a solvent having a medium particle size range of 100 to 200 nm. Further, these silver particles are obtained by binding a protective agent made of a specific amine compound. According to the present inventors, the possibility of sintering at low temperatures and the reduction in resistance of the sintered body, which are the problems of the present application, are to make the particle size range of the main silver particles within the above range, and to use an appropriate protective agent. Effectively achieved as a result of the combination with the selection. Hereinafter, the present invention will be described in more detail.
  • silver particles having a particle size of 100 to 200 nm are present in an amount of 30% or more on the basis of the number of particles with respect to the whole silver particles as solids. This is because such moderately fine silver particles contribute to low temperature sintering. It is preferable that all the silver particles contained in the paste have a particle size of 100 to 200 nm, that is, a ratio of 100%, but this need not be the case. If silver particles having a particle size of 100 to 200 nm are 30% or more, particles outside this particle size range may be present.
  • the ratio of the silver particles having a particle size of 100 to 200 nm is 30% or more, 150 ° C. or less. Sintering is possible, and the resistance value of the sintered body is low.
  • it may be a metal paste in which coarse silver particles having a particle size of more than 500 nm are mixed with silver particles having a particle size of 100 to 200 nm. Usually, coarse silver particles exceeding 500 nm (0.5 ⁇ m) are not sintered at 200 ° C. or lower. However, when silver particles having a particle diameter of 100 to 200 nm applied in the present invention are present in a certain ratio or more, the entire silver particles including such coarse particles are sintered at a low temperature.
  • the ratio of the number of silver particles having a particle diameter of 100 to 200 nm is less than 30%, sintering does not occur at 150 ° C. or lower or is insufficient.
  • all the silver particles in the metal paste have a particle size of 100 to 200 nm, that is, those having a number ratio of 100%, have the effect of the present invention.
  • the average particle diameter (number average) for all silver particles is A thickness of 60 to 800 nm is preferable.
  • the sinterability of silver particles having a particle size of 100 to 200 nm is also related to the action of a protective agent bonded to the silver particles.
  • the protective agent is a compound that binds to a part or the whole surface of metal particles suspended in a solvent, and suppresses aggregation of the metal particles.
  • the protective agent bonded to the silver particles is an amine compound having 4 to 8 carbon atoms in total.
  • a protective agent for silver particles organic substances such as carboxylic acids are generally applicable in addition to amines, but the protective agent applied in the present invention is limited to amine compounds when a protective agent other than amine is applied. This is because sintering of silver particles at 150 ° C. or lower does not occur. In this respect, even when the particle diameter of the silver particles is in the range of 100 to 200 nm, low-temperature sintering does not occur with a protective agent other than amine.
  • the total number of carbon atoms of the amine compound as a protective agent is set to 4-8 because the carbon number of the amine affects the stability and sintering characteristics of the silver particles in relation to the particle size of the silver particles. Because. This is because it is difficult for an amine having less than 4 carbon atoms to stably present silver fine particles having a particle diameter of 100 nm or more, and it is difficult to form a uniform sintered body. On the other hand, amines having more than 8 carbon atoms tend to increase the stability of silver particles excessively and increase the sintering temperature. Therefore, the protective agent of the present invention is limited to amine compounds having 4 to 8 carbon atoms in total.
  • the amine compound is preferably an amine compound having a boiling point of 220 ° C. or lower. Silver particles to which such a high-boiling amine compound is bonded are difficult to separate during sintering even if the particle size range is in an appropriate range, thus inhibiting the progress of sintering.
  • the number of amino groups in the amine compound as the protective agent (mono) amine having one amino group or diamine having two amino groups can be applied.
  • the number of hydrocarbon groups bonded to the amino group is preferably one or two, that is, primary amine (RNH 2 ) or secondary amine (R 2 NH) is preferable.
  • RNH 2 primary amine
  • R 2 NH secondary amine
  • the hydrocarbon group bonded to the amino group may be a hydrocarbon group having a cyclic structure in addition to a chain hydrocarbon having a linear structure or a branched structure. Further, oxygen may be partially included.
  • the protective agent applied in the present invention include the following amine compounds.
  • the protective agent composed of the above-described amine compound is bonded to all silver particles in the metal paste.
  • silver particles having a particle size of 100 to 200 nm are essential, but silver particles having a particle size outside this range are allowed to be mixed. Even when such silver particles having different particle diameters are mixed, it is naturally required that the protective agent for silver particles having a particle diameter of 100 to 200 nm is the above-mentioned amine compound, but it is outside the range of 100 to 200 nm.
  • the silver particles are required to have the amine compound protective agent bound thereto.
  • the compounds are not necessarily the same, and different protecting agents may be included as long as the total number of carbon atoms is 4 to 8 (for example, within the range shown in Table 1).
  • an amine compound as a protective agent is contained in an amount that is not excessive or insufficient, and is bonded to silver particles in order to ensure low-temperature sinterability.
  • the amount of the protective agent is small, the protective effect on the silver particles is insufficient, and the silver particles agglomerate during storage and the low-temperature sinterability is impaired.
  • bonds with silver particle excessively there exists a possibility that the volume shrinkage of the silver sintered compact by amine loss
  • a ratio of nitrogen concentration (mass%) to silver particle concentration (mass%) is preferably 0.0003 to 0.003. If it is less than 0.0003, the protective effect on silver particles is insufficient, and if it exceeds 0.003, the sintered body may be cracked.
  • the nitrogen concentration in the metal paste can be measured by elemental analysis (CHN analysis or the like) of the paste, and the silver particle concentration can be easily obtained from the mass of silver particles and the amount of solvent used during paste production.
  • the silver particles combined with the silver particle protective agent described above are dispersed and suspended in a solvent to form a metal paste.
  • a solvent an organic solvent having 8 to 16 carbon atoms and having an OH group in the structure and a boiling point of 280 ° C. or lower is preferable. This is because when the silver particle sintering temperature target is set to 150 ° C. or lower, it is difficult to volatilize and remove a solvent having a boiling point higher than 280 ° C.
  • this solvent examples include terpineol (C10, boiling point 219 ° C.), dihydroterpineol (C10, boiling point 220 ° C.), texanol (C12, boiling point 260 ° C.), 2,4-dimethyl-1,5-pentadiol ( C9, boiling point 150 ° C.) and 2,2,4-trimethyl-1,3-pentanediol diisobutyrate (C16, boiling point 280 ° C.).
  • a plurality of solvents may be used as a mixture, or may be used alone.
  • the solvent content is preferably 5% to 60% by mass. If it is less than 5%, the viscosity of the paste becomes too high. If it exceeds 60%, it becomes difficult to obtain a sintered body having a required thickness.
  • the metal paste according to the present invention is produced by kneading a solid containing 30% or more of silver particles having a particle diameter of 100 to 200 nm in a solvent. In order to produce a solid content made of silver particles containing 30% or more of silver particles having a particle size of 100 to 200 nm, it is required to produce silver particles while adjusting the particle size and particle size distribution.
  • the thermal decomposition method which used the silver complex as the precursor is employ
  • the thermal decomposition method uses a silver compound having thermal decomposability such as silver oxalate (Ag 2 C 2 0 4 ) as a starting material, and forms a silver complex with an organic compound that serves as a protective agent. Is heated to obtain silver particles.
  • the thermal decomposition method is also a method applied in the above-mentioned Patent Document 2.
  • the particle size adjustment is easier than other silver particle production methods such as a liquid phase reduction method (the method described in Patent Document 1), and comparatively grain size Silver particles with a uniform diameter can be produced.
  • the conventional pyrolysis method is suitable for the production of fine silver particles having an average particle diameter of several nm to several tens of nm. It was difficult to preferentially produce silver particles having a moderately large particle size range of 100 to 200 nm.
  • the present inventors consider the mechanism of silver particle formation by the pyrolysis method, and adjust the amount of water in the reaction system when the silver complex is pyrolyzed to form silver particles, thereby allowing silver having a particle size of 100 to 200 nm. The particles were preferentially manufactured.
  • the method for producing silver particles according to the present invention comprises producing a silver-amine complex as a precursor by mixing a silver compound having thermal decomposability and an amine, and heating the reaction system containing the precursor.
  • the water content of the reaction system before heating is set to 5 to 100 parts by weight with respect to 100 parts by weight of the silver compound.
  • the silver compound having thermal decomposability as a starting material is silver oxalate, silver nitrate, silver acetate, silver carbonate, silver oxide, silver nitrite, silver benzoate, silver cyanate, Silver citrate, silver lactate, etc.
  • silver oxalate Ag 2 C 2 O 4
  • silver carbonate Ag 2 CO 3
  • Silver oxalate and silver carbonate can be decomposed at a relatively low temperature without requiring a reducing agent to produce silver particles. Further, since carbon dioxide generated by the decomposition is released as a gas, no impurities remain in the solution.
  • silver oxalate is explosive in the dry state
  • water or an organic solvent (alcohol, alkane, alkene, alkyne, ketone, ether, ester, carboxylic acid, fatty acid, aromatic, amine, amide, nitrile Etc.) are preferably mixed and wetted. By making it wet, explosiveness is remarkably lowered and handling becomes easy. At this time, a mixture of 5 to 200 parts by weight of a dispersion solvent with respect to 100 parts by weight of silver oxalate is preferable.
  • the present invention since the present invention strictly regulates the amount of water in the reaction system, the mixing of water needs to be within a range not exceeding the specified amount.
  • a silver-amine complex that is a precursor of silver particles is formed by mixing and reacting the above silver compound and an amine compound.
  • an amine compound having a total carbon number of 4 to 8 is used as the amine used here.
  • the amine compound is mixed so that the ratio of the mass of the amine compound (protective agent) to the mass of silver in the silver compound (the mass of the amine compound (protective agent) / Ag mass) is 2 to 5. Adjust the amount. This is because a sufficient silver-amine complex is formed without generating an unreacted silver compound. Even if an excessive amine compound is bonded to the silver particles, it is removed by washing after the silver particles are produced.
  • a silver-amine complex is formed by the reaction between the silver compound and the amine compound, and a reaction system for producing silver particles is formed. Thereafter, the reaction system is heated to produce silver particles.
  • the amount of water in the reaction system is defined at this stage. It is considered that the water in the reaction system acts as a buffering agent that causes heating to proceed uniformly in the complex decomposition step.
  • the buffering action of water is used to relax the temperature difference in the reaction system during heating, and promote nucleation and growth of silver particles while making them uniform.
  • the water content of the reaction system needs to be in the range of 5 to 100 parts by weight with respect to 100 parts by weight of the silver compound.
  • a preferred range for the water content is 5 to 95 parts by weight, and a more preferred range is 5 to 80 parts by weight.
  • the amount of water is small (less than 5 parts by weight)
  • the particle size of the obtained silver particles is mainly fine particles of less than 100 nm, and the proportion of silver particles of 100 to 200 nm is reduced.
  • the amount of water is large (exceeding 100 parts by weight)
  • the particle size variation of the silver particles becomes too large, and the ratio of the silver particles of 100 to 200 nm tends to decrease.
  • the water content of this reaction system is the water content immediately before the heating step, and it is necessary to consider the amount of water added to the reaction system so far.
  • the amount of water added in advance is also included in the amount of water. For this reason, when only the amount added in advance to the silver compound or the homogenizing agent falls within the specified range of the water content, it can be heated as it is without separately adjusting the water content of the reaction system.
  • the amount added in advance is less than the lower limit (5 parts by weight) of the water content, it is necessary to adjust the amount of water, such as adding water separately.
  • the timing for adding water may be before the heating step, and may be added at any stage before or after the formation of the silver-amine complex.
  • the reaction system is composed of a silver-amine complex and an appropriate range of moisture, and silver particles having a suitable particle size range can be produced without other additives.
  • adjustment of the particle size distribution increase in the proportion of silver particles of 100 to 200 nm
  • addition of additives for further stabilization of the silver complex are not excluded depending on the relationship of the amine compound used. .
  • the additive applicable in the present invention is a homogenizing agent for adjusting the particle size distribution.
  • This homogenizing agent is an organic compound represented by Chemical Formula 1 having an amide as a skeleton.
  • This homogenizing agent makes the silver particle size uniform by making the stability of the silver-amine complex in the reaction system uniform and by aligning the timing of nucleation and growth when silver particles are produced by complex decomposition. Additives to align.
  • An organic compound that functions as a homogenizing agent is required to have an amide (carboxylic amide) (NC—O) in its skeleton.
  • R represents hydrogen, hydrocarbon, aminoalkyl or an amino group comprising a combination thereof
  • R ′, R ′′ represents hydrogen or hydrocarbon.
  • organic compound that is a homogenizing agent examples include urea, urea derivatives, N, N-dimethylformamide (DMF: (CH 3 ) 2 NCHO), N, N-diethylformamide (DEF: (C 2 H 5 ) 2 NCHO), N, N-dimethylacetamide (C 4 H 9 NO), N, N-dimethylpropionamide (C 5 H 11 NO), N, N-diethylacetamide (C 6 H 13 NO) Etc.
  • urea derivatives include 1,3-dimethylurea (C 3 H 8 N 2 O), tetramethylurea (C 5 H 12 N 2 O), 1,3-diethylurea (C 5 H 12 N 2 O), and the like. Is mentioned.
  • the amount is the ratio of the number of moles of the homogenizing agent (mol homogenizing agent ) to the number of moles of silver (mol Ag ) in the silver compound (mol homogenizing agent / mol Ag ). Therefore, it is preferably 0.1 or more.
  • the total addition amount is preferably 0.1 or more. If the molar ratio is less than 0.1, the effect is difficult to occur.
  • the upper limit of the molar ratio (the upper limit of the homogenizing agent) is not particularly specified, but is preferably 4 or less with respect to silver of the silver compound in consideration of the purity of the silver particles.
  • the homogenizing agent is preferably added as it is in the case of a liquid organic compound. Further, in the case of a solid compound such as urea, it may be added as a solid or may be added as an aqueous solution. However, when the aqueous solution is used, it is necessary to consider the water content of the reaction system.
  • the heating temperature at this time is preferably not less than the decomposition temperature of the silver-amine complex.
  • the decomposition temperature of the silver-amine complex varies depending on the type of amine coordinated to the silver compound, but in the case of the silver complex of the amine compound applied in the present invention, the specific decomposition temperature is 90 to 130 ° C.
  • the heating rate affects the particle size of the precipitated silver particles. Therefore, the particle size of the silver particles can be controlled by adjusting the heating rate of the heating step.
  • the heating rate in the heating step is preferably adjusted in the range of 2.5 to 50 ° C./min up to the set decomposition temperature.
  • the precipitated silver particles are recovered through solid-liquid separation and become a solid content of the metal paste. What is important here is that washing is performed so that excessive amine compounds do not bind to the recovered silver particles.
  • the silver particles are preferably washed with an alcohol having a boiling point of 150 ° C. or lower such as methanol, ethanol, propanol or the like as a solvent.
  • an alcohol having a boiling point of 150 ° C. or lower such as methanol, ethanol, propanol or the like as a solvent.
  • cleaning after adding a solvent to the solution after silver particle synthesis
  • the amount of amine removed can be controlled by the volume of solvent added and the number of washings.
  • the solvent is used in a volume of 1/20 to 3 times that of the solution after silver particle synthesis, and washed 1 to 5 times.
  • the collected silver particles can be made into a metal paste by kneading with an appropriate solvent as a solid content.
  • an appropriate solvent as a solid content.
  • the solvent those described above can be applied.
  • the production of silver particles by the above process is performed in two or more systems, and a mixture of two or more kinds of silver particles produced by them is used as a solid content, which is kneaded with a solvent to produce a metal paste. Also good.
  • the metal paste containing silver particles with controlled particle size according to the present invention can be sintered even at a low temperature range of 150 ° C. or lower, and the resulting sintered body exhibits a low resistance value equivalent to that of bulk silver. .
  • the metal paste according to the present invention can be applied as a conductive bonding material, and is also useful as a bonding material for electrical devices that handle large currents such as power devices.
  • the figure explaining the silver particle manufacturing process in this embodiment The SEM photograph which shows the form of the silver particle manufactured by this embodiment.
  • silver particles are produced while changing various conditions such as a silver compound as a raw material and an amine compound as a protective agent, and after kneading with a solvent to produce a metal paste, its thermal analysis and sintering characteristics And the resistance of the sintered compact was evaluated.
  • the outline of the manufacturing process of the silver particle in this embodiment is shown in FIG. 1, and the manufacturing process of a silver particle is demonstrated.
  • Silver Particles In this embodiment, 1.41 g of silver oxalate or 1.28 g of silver carbonate was used as a raw material silver compound so that the silver content was 1 g. When these silver compounds are used as they are, they are moistened with 0.3 g of water (21 parts by weight for 100 parts by weight of silver oxalate and 23 parts by weight for 100 parts by weight of silver carbonate). I prepared something in a state.
  • amine compounds were added to the silver compound as a protective agent to produce a silver-amine complex.
  • the silver compound and amine were mixed at room temperature and kneaded until creamed.
  • the produced silver-amine complex was optionally added in combination with a urea solution and DMF as a homogenizing agent. In consideration of the amount of water, water was sometimes added. And the water content of the reaction system was checked before heating.
  • the protective agent the example which applied oleic acid as things other than an amine is also prepared.
  • the reaction system in which the water content was confirmed was heated from room temperature to decompose the silver-amine complex and precipitate silver particles.
  • the heating temperature at this time was assumed to be 110 to 130 ° C. as the decomposition temperature of the complex, and this was set as the ultimate temperature.
  • the heating rate was 10 ° C./min.
  • Low-temperature sintering test The metal paste produced above was sintered at a low temperature, and the presence / absence of sintering, electrical resistance of the sintered body, and adhesion (bonding force) were evaluated.
  • 50 mg of each metal paste was applied to a Si substrate (with gold plating) (targeted to a film thickness of 50 ⁇ m), the temperature was raised to 150 ° C. at a rate of 2 ° C./min, and the temperature was increased to 150 ° C. At that stage, it was held for 2 hours and sintered.
  • the sintered body was evaluated by first observing SEM and evaluating the presence or absence of the sintered body formation, and then measuring the volume resistivity.
  • metal pastes a, b, and c having a particle size ratio of 100 to 200 nm and an average particle size of 20 to 30 nm are easily obtained. Sintered. On the other hand, metal pastes m, n, and o that tend to have a large average particle size are difficult to sinter. From these results, it can be said that there is a temporary correlation between the particle size and the sintering temperature. However, the metal pastes a to c form a sintered body, but have a high resistance value and poor adhesion. Moreover, although sintered, many cracks were generated in the sintered body and there were some powdered portions.
  • the resistance value it is considered that the resistance is larger than the resistance value (1.6 ⁇ ⁇ cm) of the bulk silver due to the voids called cracks.
  • the influence of the presence of cracks can be considered on the adhesion, but in the first place, it is considered that the metal paste mainly composed of these fine silver particles is not sufficiently sintered (details will be described later). This will be explained by the results of thermal behavior studies). From these results, it can be said that it is not preferable to discuss only the average particle size in order to achieve both low-temperature sinterability of silver particles and low resistance of the sintered body.
  • metal pastes (d to f, h, j to l) which contain silver particles having a suitable particle size (particle size of 100 to 200 nm) and suitable protective agents have good low-temperature sinterability. There were no cracks. And resistance value is also a value close
  • the metal paste g preferably has a silver particle ratio of 100 to 200 nm, but since hydroxyethylaminopropylamine (boiling point: 250 ° C.) with a boiling point exceeding 220 ° C. is applied, the sinterability at low temperatures is It can be said that it is inferior.
  • metal paste i to which oleic acid was applied as a protective agent instead of an amine compound although a silver particle ratio of 100 to 200 nm was suitable, low-temperature sintering could not be performed.
  • the metal paste (a to c) mainly composed of fine silver particles (particle size 20 to 30 nm) sinters, but many cracks occur in the sintered body. It was confirmed that the adhesion was also poor. On the other hand, the metal paste mainly composed of particles having a particle diameter of 100 to 200 nm according to the present invention did not cause any problems in sintering and cracks. Here, it was decided to conduct an analysis to confirm the difference in thermal behavior of each metal paste and the crack generation mechanism.
  • the thermal history (held at 150 ° C. for 2 hours) performed in the low-temperature sintering test is close to the actual usage of the metal paste, but there is no change in the heating temperature. Not suitable for analysis of thermal behavior. Therefore, in this embodiment, TG-DTA analysis (differential thermal analysis) for heating the metal paste at a constant temperature increase rate was performed, and the number of exothermic peaks and the generated temperature due to the sintering of silver particles were confirmed.
  • the rate of temperature rise is 5 ° C./min to 20 ° C./min.
  • the measurement temperature range was from room temperature to 500 ° C., and the measurement was performed at a rate of temperature increase of 10 ° C./min.
  • FIG. 4 shows DTA curves of pastes c, f, i, and m as a representative example. Table 4 shows the number of exothermic peaks due to the sintering of silver particles and the measurement results of the generated temperature for the DTA curve measured for each metal paste.
  • the metal paste (a to c) mainly composed of fine silver particles having a particle size of 20 to 30 nm has an exothermic peak at less than 200 ° C. (180 ° C., 190 ° C.), and more than 200 ° C. ( Even at 210 ° C. and 230 ° C., exothermic peaks appear.
  • the exothermic peak at low temperature is expected in these metal pastes, which are considered to be sintered at low temperature due to the nanosize effect.
  • a plurality of exothermic peaks appear in this way because the sintering behavior of fine silver particles proceeds in multiple stages.
  • the metal paste (d to f, h, j to l) mainly composed of particles having a particle diameter of 100 to 200 nm according to the present invention exhibits a characteristic behavior in the DTA results. That is, in this metal paste, only one exothermic peak derived from the silver particle sintering of the DTA curve appears in a temperature range below 200 ° C. (180 ° C., 190 ° C.). The occurrence of only one exothermic peak indicates that the silver particles are completely sintered in one stage. The phenomenon in which a single exothermic peak appears in this low temperature range is unique.
  • the low-temperature sintering test of this embodiment is equivalent to the heating conditions (fixed at 150 ° C. and held for a certain period of time) in actual use. From this test result, the metal paste suitable for this embodiment is It can be understood that the low temperature sintering property is excellent.
  • FIG. 5 is an SEM photograph of 180 ° C. and 210 ° C. sintered bodies of pastes c and f.
  • 180 ° C. which is the first stage, no cracks occurred in the sintered bodies for both pastes c and f.
  • 210 ° C. corresponding to the second stage for c many cracks are generated only in c. That is, the crack in the paste c is generated during the second stage sintering. It can be said that such a crack does not occur in the paste f not subjected to multi-stage sintering.
  • FIG. 6 is an enlarged view of the photograph of 210 ° C. heating in FIG. According to this photograph, the pastes c and f are very similar in shape and particle size (about 500 nm) of individual particles constituting the sintered body. From this, the hypothesis holds that the diameter of the thermally stable unit particles (units) in the silver sintered body is roughly determined regardless of the particle diameter of the silver particles before sintering.
  • the results of DTA analysis confirm that it is necessary to select an appropriate amine as a protective agent for the silver particles.
  • the temperature is as high as 200 ° C. or more (metal paste i) although there is only one exothermic peak due to sintering.
  • the metal paste g has a silver particle ratio of 100 to 200 nm in particle size, but an amine compound with a high boiling point was applied, so that an exothermic peak appeared at 200 ° C. or higher. Even when the particle size is too large, the exothermic peak does not appear unless it is 200 ° C. or higher (metal paste m).
  • the silver paste according to the present invention acquires low-temperature sinterability by adjusting the particle size range of the main silver particles.
  • the silver sintered body formed according to the present invention has a low resistance and a sufficient bonding strength. It can be widely used as a wiring material, a bonding material or a heat conduction material that requires a sintering process at a low temperature.

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PCT/JP2015/054723 2014-02-25 2015-02-20 低温焼結性に優れる銀ペースト及び該銀ペーストの製造方法 WO2015129562A1 (ja)

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DE112015000957.4T DE112015000957B4 (de) 2014-02-25 2015-02-20 Silberpaste mit hervorragender Niedertemperatur-Sinterbarkeit und Verfahren zur Herstellung dieser Silberpaste
CN201580010191.2A CN106062886B (zh) 2014-02-25 2015-02-20 低温烧结性优异的银浆料及该银浆料的制造方法
KR1020187009140A KR20180036799A (ko) 2014-02-25 2015-02-20 저온 소결성이 우수한 은 페이스트 및 당해 은 페이스트의 제조 방법
KR1020167023468A KR101866111B1 (ko) 2014-02-25 2015-02-20 저온 소결성이 우수한 은 페이스트 및 당해 은 페이스트의 제조 방법

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