WO2019026799A1 - Composition destinée à une liaison de métal, stratifié de liaison de métal et dispositif de commande électrique - Google Patents
Composition destinée à une liaison de métal, stratifié de liaison de métal et dispositif de commande électrique Download PDFInfo
- Publication number
- WO2019026799A1 WO2019026799A1 PCT/JP2018/028293 JP2018028293W WO2019026799A1 WO 2019026799 A1 WO2019026799 A1 WO 2019026799A1 JP 2018028293 W JP2018028293 W JP 2018028293W WO 2019026799 A1 WO2019026799 A1 WO 2019026799A1
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- WO
- WIPO (PCT)
- Prior art keywords
- metal
- composition
- bonding
- metal bonding
- particles
- Prior art date
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
- H01L2224/31—Structure, shape, material or disposition of the layer connectors after the connecting process
- H01L2224/32—Structure, shape, material or disposition of the layer connectors after the connecting process of an individual layer connector
- H01L2224/321—Disposition
- H01L2224/32151—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
- H01L2224/32221—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
- H01L2224/32225—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/42—Wire connectors; Manufacturing methods related thereto
- H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
- H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
- H01L2224/4805—Shape
- H01L2224/4809—Loop shape
- H01L2224/48091—Arched
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/73—Means for bonding being of different types provided for in two or more of groups H01L2224/10, H01L2224/18, H01L2224/26, H01L2224/34, H01L2224/42, H01L2224/50, H01L2224/63, H01L2224/71
- H01L2224/732—Location after the connecting process
- H01L2224/73251—Location after the connecting process on different surfaces
- H01L2224/73265—Layer and wire connectors
Definitions
- the present invention relates to a metal bonding composition, a metal bonding laminate, and an electrical control device.
- a bonding material such as a solder, a conductive adhesive, a silver paste, an anisotropic conductive film or the like is used for mechanical, electrical and / or thermal bonding of metal parts.
- These bonding materials may be used not only for metal parts but also for bonding ceramic parts, resin parts and the like.
- applications of the bonding material include applications in which a light emitting element such as an LED is bonded to a substrate, applications in which a semiconductor chip is bonded to a substrate, and applications in which those substrates are further bonded to a heat dissipation member.
- Examples of prior art documents related to bonding materials include Patent Documents 1 to 3.
- Patent Document 1 discloses a bonding composition containing inorganic particles and an organic component, wherein the inorganic particles irreversibly exceed the linear expansion coefficient of the inorganic substance constituting the inorganic particles as the temperature rises.
- a bonding composition is disclosed which is characterized by expanding.
- Patent Document 2 as main silver particles, coated with a carboxylic acid having 6 or less carbon atoms and coated with nanosilver particles having an average primary particle diameter of 10 to 30 nm and secondary silver particles, coated with a carboxylic acid having 6 or less carbon atoms
- Silver particles composed of nanosilver particles having an average primary particle size of 100 to 200 nm and submicron silver particles having an average primary particle size of 0.3 to 3.0 ⁇ m, and a low boiling point solvent having a boiling point of 100 to 217 ° C.
- a bonding material comprising two different polar solvents having a high boiling point of 230 to 320 ° C.
- the average primary particle size is a TEM image taken at a magnification of 300,000. Is the average of the particle sizes of 200 or more particles measured by circular image analysis to identify individual particles, and the content of the silver particles is 95 with respect to the total bonding material amount.
- the main silver particle is 10 to 40% by mass with respect to the total bonding material amount, and the content ratio of the solvent having the lower boiling point and the solvent having the higher boiling point among the two types of solvents is A bonding material is disclosed, which is characterized in that it is 3: 5 to 1: 1 in mass ratio.
- Patent Document 3 metal submicron particles having an average primary particle size (D50 diameter) of 0.5 to 3.0 ⁇ m and an average primary particle size of 1 to 200 nm, which are measured by a microtrack particle size distribution measuring apparatus.
- a bonding material including metal nanoparticles coated with a fatty acid having 6 carbon atoms and a dispersion medium for dispersing these.
- the present inventor has researched and developed a metal bonding composition containing metal particles in order to produce a metal bonding material having high bonding strength, but metal bonding is caused by a thermal load applied in a heat cycle test or the like. Cracks may occur in the material, and there is room for improvement in durability.
- the present invention has been made in view of the above-mentioned present situation, and a composition for metal bonding suitable for forming a metal bonding material excellent in durability against a thermal load applied in a heat cycle test or the like, and for the metal bonding.
- An object of the present invention is to provide a metal bonding laminate and an electric control device in which bonding of metal surfaces is performed by firing a composition.
- the inventors of the present invention conducted various studies on a metal bonding composition suitable for forming a metal bonding material excellent in durability against a thermal load applied in a heat cycle test or the like.
- the tensile breaking stress of the film after firing can be improved by combining nanoparticles of particle size 1 to 99 nm with submicron particles of particle size 100 to 999 nm and / or micron particles of particle size 1 to 999 ⁇ m. Found out.
- the heat cycle test is performed by adjusting the particle diameter of silver particles to be added to the metal bonding composition, the kind of the dispersion medium, and the like so that the tensile breaking stress of the film when fired at 275 ° C. is 100 MPa or more. It has been found that the increase of the void ratio (porosity) due to the thermal load to be applied by etc. is suppressed, and a metal bonding material excellent in durability can be formed, and the present invention is completed.
- the composition for metal bonding of the present invention is a composition for metal bonding used for firing and bonding metal surfaces, and the composition for metal bonding contains silver particles and a dispersion medium, and the silver
- the particles comprise nanoparticles having a particle size of 1 to 99 nm and submicron particles having a particle size of 100 to 999 nm and / or micron particles having a particle size of 1 to 999 ⁇ m. It is characterized in that the breaking stress is 100 MPa or more.
- the silver particles preferably include the nanoparticles and the submicron particles, and more preferably, the mass ratio of the nanoparticles to the submicron particles is 4: 6 to 7: 3.
- the metal bonding laminate of the present invention is a metal bonding laminate including a metal bonding material for bonding a first metal surface and a second metal surface, and the metal bonding material is a composition for metal bonding of the present invention. It is characterized in that it is a sintered body of an object.
- At least one of the first metal surface and the second metal surface is a surface of a substrate or a plated layer made of Cu, Ag or Au.
- the first metal surface is preferably part of a semiconductor chip, and the second metal surface is preferably part of a substrate.
- the electric control device of the present invention is characterized by comprising the metal bonding laminate of the present invention.
- a metal bonding composition suitable for forming a metal bonding material excellent in durability against a thermal load applied in a heat cycle test or the like, and a metal surface by firing the metal bonding composition.
- the present invention can provide a metal-bonded laminate and an electrical control device in which bonding is performed.
- the composition for metal bonding according to the present embodiment is a composition for metal bonding used for firing and bonding metal surfaces, and the composition for metal bonding contains silver particles and a dispersion medium, and The silver particles contain nanoparticles with a particle size of 1 to 99 nm and submicron particles with a particle size of 100 to 999 nm and / or micron particles with a particle size of 1 to 999 ⁇ m. It is characterized in that a tensile breaking stress is 100 MPa or more.
- the composition for metal bonding has a tensile breaking stress of 100 MPa or more when fired at 275 ° C.
- the firing of the film may be performed under no pressure conditions.
- the baking time of a film is 60 minutes or more. If the tensile breaking stress is less than 100 MPa, a high thermal stress is generated in the heat cycle test in which the upper limit temperature is set to a high temperature such as 175 ° C. or 200 ° C., and therefore, the metal bonding material is highly cracked.
- the upper limit of the tensile breaking stress is not particularly limited, and may be, for example, 500 MPa.
- FIG. 1 is a flow diagram for explaining a method of producing a test piece for measuring the tensile breaking stress of a metal bonding composition.
- FIG. 2 is a schematic plan view showing the shape and dimensions (unit: mm) of a test piece for measuring the tensile breaking stress of a metal bonding composition.
- the baking treatment in the reflow furnace is performed in the air, and the temperature is raised from room temperature to a maximum temperature of 275 ° C. at a temperature rising rate of 3.8 ° C./min, and then held at 275 ° C. for 60 minutes.
- no pressure is applied and no pressure is applied.
- no pressure means joining without applying a load other than the weight of the object to be joined such as a semiconductor chip, and in the present measuring method, the actual joining state (object The state where the joined body is placed is reproduced. (4) As shown in FIG.
- the fired composition for metal bonding 52 is taken out from the reflow furnace, and then peeled off from the slide glasses 51 and 53 to make a test piece 54 of a tensile test.
- the tensile test is carried out at a measurement speed of 0.72 mm / min using an Instron universal tensile tester 5969. The tensile breaking stress when the test piece 54 breaks is measured.
- the measurement of the tensile breaking stress is performed on the film fired at 275 ° C.
- the dispersion medium solvent
- the organic components other than the dispersion medium such as the dispersant used for dispersing the silver particles are volatilized or decomposed. It volatilizes, but since silver particles are excellent in low-temperature sinterability, silver after removal to organic components in the composition for metal bonding and necking (partial fusion) of particles when fired up to 275 ° C. Sintering of the particles can proceed quickly.
- the composition for metal joining of this embodiment is used by baking at 275 degreeC.
- the mass reduction rate after firing is preferably 6 to 20%, more preferably 8 to 15%, and still more preferably 11 to 12%.
- the mass reduction rate can be calculated from the results of differential thermal analysis (TG-DTA). According to TG-DTA, it is possible to confirm the presence or absence of a reaction (mainly combustion / oxidative decomposition) and the end point of the reaction.
- a method of reducing the crystal grain size a method of including nanoparticles in silver particles blended in a composition for metal bonding, increasing the ratio thereof, and a method of shortening the time during which silver particles are sintered Can be mentioned.
- the ratio of the nanoparticles in the silver particles mixed in the metal bonding composition is increased, the necking portion between the silver particles can be increased.
- Shortening of the time for sintering of the silver particles the progress of fusion between the silver particles can be suppressed. Shortening of the time that sintering of the silver particles occurs is also achieved by delaying the removal of the organic components incorporated in the metal bonding composition.
- a method of adjusting the tensile breaking stress of the film when fired at 275 ° C. a method of increasing the ratio of nanoparticles in silver particles to be added to the composition for metal bonding, a dispersing agent and a dispersing medium
- the method of changing the type of is preferable.
- the dispersion medium those which volatilize before the silver particles sinter are preferable. Further, it is preferable to reduce the amount of solvent remaining before the firing step.
- the metal bonding composition is not particularly limited as long as it contains silver particles and a dispersion medium, but is preferably in the form of a paste so as to be easily applied.
- metals whose ionization sequence is nobler than hydrogen that is, particles of gold, copper, platinum, palladium, etc. may be used in combination to make migration difficult to occur.
- the silver particles are nanoparticles (also referred to as nanosilver particles) having a particle diameter of 1 to 99 nm, submicron particles having a particle diameter of 100 to 999 nm and / or micron particles (also referred to as micron silver particles) having a particle diameter of 1 to 999 ⁇ m.
- the nanoparticles may be dispersed in the metal bonding composition separately from the submicron particles or micron particles, or may be attached to at least a part of the surface of the submicron particles or micron particles.
- it is preferable that a nanoparticle, a submicron particle, and a micron particle have a peak of independent particle size distribution, respectively.
- the average particle size of the silver particles can be measured by Dynamic Light Scattering, small-angle X-ray scattering, or wide-angle X-ray diffraction, and is suitable for measuring the particle size of micron particles. is there.
- the "average particle diameter" refers to the dispersion median diameter.
- Other methods of measuring the average particle diameter include a method of calculating the arithmetic mean value of the particle diameter of about 50 to 100 particles from a photograph taken using a scanning electron microscope or a transmission electron microscope. , Is suitable for measuring the particle size of the nanoparticles.
- the average particle diameter of the nanoparticles is not particularly limited as long as the effects of the present invention are not impaired. If nanoparticles having an average particle diameter of 1 nm or more are used as silver particles having a small diameter, a metal bonding composition capable of forming a good metal bonding material can be obtained, and the production of silver particles is not expensive and practical. is there. Moreover, if it is 99 nm or less, the dispersibility of a nanoparticle does not change easily with time, and it is preferable.
- the silver particles preferably contain nanoparticles and submicron particles, and more preferably the weight ratio of nanoparticles to submicron particles contained in the silver particles is 4: 6 to 7: 3. If the mass ratio of nanoparticles to submicron particles is less than 4: 6 (the mass ratio of nanoparticles is less than 40%), the particles are less likely to be connected to each other, and the bonding strength between particles (equivalent to tensile strength) decreases. There is a risk that cracks may occur early in the heat cycle test.
- the shrinkage at the time of firing becomes large, whereby the sintered body of the composition for metal bonding is There is a possibility that the percentage of void (air gap) may become too high.
- the silver particles preferably contain nanoparticles and micron particles, and the mass ratio of nanoparticles to micron particles contained in the silver particles is more preferably 7: 3 to 8: 2. If the mass ratio of nanoparticles to micron particles is less than 7: 3 (the mass ratio of nanoparticles is less than 70%), the tensile strength may be reduced, which may cause early cracking in the heat cycle test. If the mass ratio of nanoparticles to micron particles exceeds 8: 2 (the mass ratio of nanoparticles exceeds 80%), the proportion of voids (voids) in the sintered body of the composition for metal bonding may be too high. There is.
- the average particle diameter of the above-mentioned micron particles is not particularly limited as long as the effects of the present invention are not impaired, but it is preferably 1 to 20 ⁇ m.
- micron particles having an average particle diameter of 1 to 20 ⁇ m volume shrinkage due to sintering can be reduced, and a homogeneous and dense bonding material can be obtained.
- submicron particles having an average particle size of less than 1 ⁇ m are used as large-sized silver particles, sintering proceeds at a low temperature, but as sintering between particles proceeds, volume shrinkage increases as the average particle diameter increases. There is a possibility that the bonded body can not follow the volume contraction.
- the average particle diameter of the micron particles is more preferably 1 to 10 ⁇ m.
- the silver particles can be obtained, for example, by mixing a metal ion source and a dispersing agent and reducing the mixture.
- the dispersion medium is not particularly limited as long as it can disperse the silver particles, and examples thereof include organic solvents such as hydrocarbons, alcohols, and carbitols.
- the dispersion medium is preferably volatile during the step of applying the metal bonding composition, and is preferably less volatile at room temperature.
- hydrocarbon an aliphatic hydrocarbon, cyclic hydrocarbon, an alicyclic hydrocarbon etc. are mentioned, You may use each independently and may use 2 or more types together.
- aliphatic hydrocarbon examples include saturated or unsaturated aliphatic carbonized hydrocarbons such as tetradecane, octadecane, heptamethylnonane, tetramethylpentadecane, hexane, heptane, octane, nonane, decane, tridecane, methylpentane, normal paraffin, isoparaffin, etc. Hydrogen is mentioned.
- cyclic hydrocarbon toluene, xylene etc. are mentioned, for example.
- Examples of the above-mentioned alicyclic hydrocarbon include limonene, dipentene, terpinene, terpinene (also referred to as terpinene), nesol, sinene, orange flavor, terpinolene, terpinolene (also referred to as terpinolene), ferandrene, mentadiene, tereben, dihydro
- Examples thereof include simen, musulene, isoterpinene, isoterpinene (also referred to as isoterpinene), clitormen, kautuzin, kajepten, eulimen, pinene, turpent, mentane, pinan, terpene, cyclohexane and the like.
- the alcohol is a compound containing one or more OH groups in the molecular structure, and includes aliphatic alcohols, cyclic alcohols and alicyclic alcohols, which may be used alone or in combination of two or more. Good.
- a part of the OH group may be derived to an acetoxy group or the like within the range not impairing the effects of the present invention.
- Examples of the above aliphatic alcohols include heptanol, octanol (1-octanol, 2-octanol, 3-octanol etc.), decanol (1-decanol etc.), lauryl alcohol, tetradecyl alcohol, cetyl alcohol, 2-ethyl-1 -Saturated or unsaturated C6-30 aliphatic alcohols such as hexanol, octadecyl alcohol, hexadecenol, oleyl alcohol etc. may be mentioned.
- Examples of the cyclic alcohol include cresol and eugenol.
- alicyclic alcohol for example, cycloalkanol such as cyclohexanol, terpineol (including ⁇ , ⁇ , ⁇ isomers or any mixture thereof), and terpene alcohol such as dihydroterpineol (monoterpene alcohol etc.) And dihydroterpineol, myrtenol, sobrerole, menthol, carveol, perillyl alcohol, pinocarbeole, sobrerol, verbenol and the like.
- cycloalkanol such as cyclohexanol, terpineol (including ⁇ , ⁇ , ⁇ isomers or any mixture thereof)
- terpene alcohol such as dihydroterpineol (monoterpene alcohol etc.)
- dihydroterpineol myrtenol, sobrerole, menthol, carveol, perillyl alcohol, pinocarbeole, sobrerol, verbenol and
- carbitols examples include butyl carbitol, butyl carbitol acetate, hexyl carbitol and the like.
- the initial content in the case of containing the dispersion medium in the composition for metal bonding may be adjusted according to desired characteristics such as viscosity, and the initial content of the dispersion medium in the composition for metal bonding is 1 to 30 It is preferable that it is mass%. When the initial content of the dispersion medium is 1 to 30% by mass, the effect of adjusting the viscosity can be obtained within the range in which the composition for metal bonding can be used easily. A more preferable initial content of the dispersion medium is 1 to 20% by mass, and a further preferable initial content is 1 to 15% by mass.
- hexyl carbitol and butyl carbitol acetate are preferable. It is preferable that 50 mass% or more of hexyl carbitol is contained in the dispersion medium. Further, the solid content concentration of the above-mentioned composition for metal bonding is preferably 88 to 93% by mass. If these conditions are satisfied, the viscosity can be adjusted to an appropriate range without decreasing the bonding strength and the void fraction, and a metal bonding composition having excellent printability with a metal mask can be obtained. Moreover, since the temporal stability of the viscosity can be secured, the pot life of the metal bonding composition can be extended.
- the metal bonding composition may contain an organic component other than the dispersion medium.
- the organic components are not particularly limited, and additives used to adjust the dispersibility of silver particles, the viscosity, adhesion, drying, surface tension, and coating properties (printability) of the composition for metal bonding, etc. Is used.
- an amine, carboxylic acid, a polymer dispersing agent, unsaturated hydrocarbon etc. are mentioned, for example.
- Amines and carboxylic acids contribute to the stability of silver particles in a storage state, because the functional group adsorbs to the surface of silver particles with appropriate strength and prevents the silver particles from contacting each other. It is thought that the additive adsorbed on the surface of the silver particles moves and / or volatilizes from the surface of the silver particles during heating, thereby promoting fusion between the silver particles and bonding with the substrate.
- the polymer dispersant can maintain dispersion stability without losing the low-temperature sinterability of silver particles by attaching an appropriate amount to at least a part of silver particles.
- An organic component adheres to at least a part of the surface of the silver particle (that is, at least a part of the surface of the silver particle is covered with an organic protective layer composed of the organic component), and an organic component (organic protection)
- the layer preferably contains an amine.
- the amine can be suitably used as an organic protective layer because the functional group is adsorbed on the surface of silver particles with an appropriate strength.
- the above amine is not particularly limited, and examples thereof include alkylamines (such as linear alkylamines and side chains) such as oleylamine, butylamine, pentylamine, hexylamine, hexylamine and octylamine; N- Alkoxyamines such as (3-methoxypropyl) propane-1,3-diamine, 2-methoxyethylamine, 3-methoxypropylamine, 3-ethoxypropylamine; cycloalkylamines such as cyclopentylamine and cyclohexylamine; allylamines such as aniline Etc., secondary amines such as dipropylamine, dibutylamine, piperidine and hexamethyleneimine, and tertiary amines such as tripropylamine, dimethylpropanediamine, cyclohexyldimethylamine, pyridine and quinoline It is possible to have.
- alkylamines such
- the amine is preferably an amine having about 2 to 20 carbon atoms, more preferably an amine having 4 to 12 carbon atoms, and still more preferably an amine having 4 to 7 carbon atoms.
- the amine having 4 to 7 carbon atoms heptylamine, butylamine, pentylamine and hexylamine can be exemplified. Since the amine having 4 to 7 carbon atoms moves and / or volatilizes at relatively low temperature, the low temperature sinterability of silver particles can be fully utilized.
- the amine may be linear, branched, or have a side chain.
- organic components when these organic components are chemically or physically bonded to silver particles, it is also considered to be converted into anions or cations, and in this embodiment, ions derived from these organic components are considered. And complexes are also included in the above organic components.
- the amine may be, for example, a compound containing a functional group other than an amine, such as a hydroxyl group, a carboxyl group, an alkoxy group, a carbonyl group, an ester group or a mercapto group.
- a functional group other than an amine such as a hydroxyl group, a carboxyl group, an alkoxy group, a carbonyl group, an ester group or a mercapto group.
- the above amines may be used alone or in combination of two or more.
- the boiling point at normal temperature is preferably 300 ° C. or less, more preferably 250 ° C. or less.
- the compound which has an at least 1 carboxyl group can be used widely, for example, a formic acid, an oxalic acid, an acetic acid, a hexanoic acid, an acrylic acid, an octylic acid, levulinic acid, an oleic acid etc. are mentioned.
- a part of carboxyl groups of the carboxylic acid may form a salt with the metal ion.
- 2 or more types of metal ions may be contained.
- the carboxylic acid may be, for example, a compound containing a functional group other than a carboxyl group, such as an amino group, a hydroxyl group, an alkoxy group, a carbonyl group, an ester group or a mercapto group.
- the number of carboxyl groups is preferably equal to or greater than the number of functional groups other than carboxyl groups.
- the carboxylic acids may be used alone or in combination of two or more.
- the boiling point at normal temperature is preferably 300 ° C. or less, more preferably 250 ° C. or less.
- the amine and the carboxylic acid form an amide group.
- An amide group may be contained in the organic component because the amide group is also appropriately adsorbed on the surface of silver particles.
- composition ratio (mass) in the case of using an amine and a carboxylic acid in combination can be optionally selected in the range of 1/99 to 99/1, but is preferably 20/80 to 98/2. Preferably, it is 30/70 to 97/3.
- a commercially available polymer dispersant can be used as the above-mentioned polymer dispersant.
- Commercially available polymer dispersants include, for example, Solsperse (SOLSPERSE) 11200, Solsparse 13940, Solsparse 16000, Solsparse 17000, Solsparse 18000, Solsparse 20000, Solsparse 24000, Solsparse 26000, Solsparse 27000, Solsparse 28000, Solsparse 54000 (or more, Japan Lubrisol Corporation); DISPERBIC (DISPERBYK) 142; DISPERBIC 160, DISPERBIC 161, DISPERBIC 162, DISPERBIC 163, DISPERBIC 166, DISPERBIC 170, DISPERBIC 180, DISPERBIC 182, DISPERBIC 184, DISPERBIC Bic 190, Disperbic 2155 ( Above, made by Bick Chemie Japan Ltd .;
- Solsparse 11200 From the viewpoint of low-temperature sinterability and dispersion stability, it is preferable to use Solsparse 11200, Solsparse 13940, Solsparse 16000, Solsparse 17000, Solsparse 18000, Solsparse 28000, Solsparse 54000, Disperbic 142 or Disperbic 2155.
- the content of the polymer dispersant is preferably 0.03 to 15% by mass.
- the content of the polymer dispersant is 0.1% by mass or more, the dispersion stability of the obtained composition for metal bonding is improved, but when the content is too large, the bonding property is lowered.
- the more preferable content of the polymer dispersant is 0.05 to 3% by mass, and the more preferable content is 0.1 to 2% by mass.
- Examples of the unsaturated hydrocarbon include ethylene, acetylene, benzene, acetone, 1-hexene, 1-octene, 4-vinylcyclohexene, cyclohexanone, terpene alcohols, allyl alcohol, oleyl alcohol, 2-palmitoleic acid, and petroselinic acid. And oleic acid, elaidic acid, thianicic acid, ricinoleic acid, linoleic acid, linoleic acid, linolenic acid, arachidonic acid, acrylic acid, methacrylic acid, gallic acid, salicylic acid and the like.
- unsaturated hydrocarbons having a hydroxyl group are preferably used.
- the hydroxyl group is easily coordinated to the surface of the silver particle, and aggregation of the silver particle can be suppressed.
- the unsaturated hydrocarbon having a hydroxyl group include terpene alcohols, allyl alcohol, oleyl alcohol, thianic acid, ricinoleic acid, gallic acid, salicylic acid and the like.
- they are unsaturated fatty acids having a hydroxyl group, and examples thereof include thianic acid, ricinoleic acid, gallic acid, salicylic acid and the like.
- an amine or a carboxylic acid having a boiling point of 150 to 300 ° C. is preferable, and in particular, levulinic acid is particularly suitably used.
- Activators, thickeners, surface tension modifiers and the like may be included.
- the resin component examples include polyester resins, polyurethane resins such as blocked isocyanate, polyacrylate resins, polyacrylamide resins, polyether resins, melamine resins, terpene resins, etc. These may be used alone or in combination of two or more.
- organic solvent except for those mentioned above as the dispersion medium, for example, methyl alcohol, ethyl alcohol, n-propyl alcohol, 2-propyl alcohol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,2,6-hexanetriol, 1-ethoxy-2-propanol, 2-butoxyethanol, ethylene glycol, diethylene glycol, triethylene glycol, weight average molecular weight in the range of 200 to 1,000 Polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol having a weight average molecular weight in the range of 300 to 1,000, N, N-dimethylformamide, dimethyl sulfoxide, - methyl-2-pyrrolidone, N, N- dimethylacetamide, glycerin, acetone and the like may be used each of which alone or in combination of two or more.
- the thickener examples include clay minerals such as clay, bentonite and hectorite, polyester emulsion resins, acrylic emulsion resins, polyurethane emulsion resins, emulsions such as blocked isocyanate, methyl cellulose, carboxymethyl cellulose and hydroxyethyl cellulose, There may be mentioned cellulose derivatives such as hydroxypropyl cellulose and hydroxypropyl methylcellulose, polysaccharides such as xanthan gum and guar gum, etc. These may be used alone or in combination of two or more.
- the surfactant is not particularly limited, and any of anionic surfactants, cationic surfactants, and nonionic surfactants can be used, and examples thereof include alkyl benzene sulfonates, quaternary ammonium salts and the like. Be Fluorine-based surfactants are preferred because the effect can be obtained with a small amount of addition.
- the content of the organic component in the composition for metal bonding of the present embodiment is preferably 5 to 50% by mass.
- the content is 5% by mass or more, the storage stability of the composition for metal bonding tends to be improved, and when the content is 50% by mass or less, the conductivity of the composition for metal bonding tends to be good.
- a more preferable content of the organic component is 5 to 30% by mass, and a further preferable content is 5 to 15% by mass.
- the composition for metal bonding of this embodiment is used for firing and bonding metal surfaces.
- a metal bonding laminate including a metal bonding material for bonding a first metal surface and a second metal surface, wherein the metal bonding material is a sintered body of a sintered body of the composition for metal bonding of the present invention.
- Laminates are also an aspect of the present invention. That is, in the metallurgical laminate according to the present embodiment, the first bonding body having the first metal surface and the second bonding body having the second metal surface bake the metal bonding composition. It bonds by the metal bonding material which consists of a silver particle sintered layer obtained by making it bind.
- the types of the first and second objects to be joined are not particularly limited, but preferably they have heat resistance not to be damaged by the temperature at the time of heat sintering of the metal bonding composition, It may be rigid or flexible. Moreover, the shape and thickness of a 1st to-be-joined body and a 2nd to-be-joined body are not specifically limited, It can select suitably.
- the type of the metal junction laminate is not particularly limited, for example, a power semiconductor element (power device) is preferable.
- the first metal surface is part of the semiconductor chip and the second metal surface is part of the substrate.
- at least one of the first metal surface and the second metal surface is a surface of a substrate or a plated layer made of Cu, Ag or Au.
- first to-be-bonded body and / or the second to-be-bonded body may be subjected to surface treatment in order to enhance the adhesion with the silver particle sintered layer.
- surface treatment include dry treatments such as corona treatment, plasma treatment, UV treatment and electron beam treatment, and a method of providing a primer layer and a conductive paste-receptive layer on an object to be bonded.
- FIG. 3 is a schematic cross-sectional view showing the configuration of a power device which is an example of a metal bond laminate.
- the lower surface of the power semiconductor chip (second bonded body) 11 and the upper surface of the copper-clad insulating substrate (first bonded body) 13 are bonded by the metal bonding material 12.
- the power semiconductor chip 11 has a main body made of Si, SiC, GaN or the like, and the lower surface thereof is plated with Au.
- the metal bonding material 12 is a silver particle sintered layer obtained by firing a metal bonding composition containing silver particles and an organic component.
- the copper-clad insulating substrate 13 has a Cu layer 13b plated with Ag on both sides of a base 13a made of silicon nitride or the like. In some cases, the Cu layer 13b is not plated with Ag.
- a heat dissipating material 14 and a heat sink 15 are attached in order to release the heat generated in the power semiconductor chip 11. Arrows in FIG. 3 indicate heat release paths. Further, a wire bond 16 is attached to the upper portion of the power semiconductor chip 11 in order to supply power to the power semiconductor chip 11.
- the metal bonding material 12 composed of the silver particle sintered layer can strongly bond the power semiconductor chip 11 to the copper-clad insulating substrate 13 mechanically, electrically and thermally.
- the silver particles are nanometer-sized particles, they can be sintered at low temperatures due to the melting point depression specific to the nanoparticles, and high conductivity and thermal conductivity close to those of metal foils can be realized.
- solder is used as the metal bonding material 12 as in the prior art
- bonding is performed by melting and solidifying the solder.
- the bonding temperature of the metal bonding material 12 is the melting point of the solder, and the heat resistant temperature (usable temperature) of the metal bonding material 12 is lower than the melting temperature (the bonding temperature) of the solder.
- long-term reliability means that the mechanical properties and the like of the metal bonded body are maintained for a long time, and, for example, the mechanical properties and the like of the metal bonded body do not easily deteriorate even by applying a large number of heat cycles. It means that.
- the silver particle sintered layer is formed, for example, through the following steps (1) to (4), using the metal bonding composition as a raw material.
- the composition for metal joining is apply
- the term "application” is a concept including the case of applying the metal bonding composition in a planar manner and the case of applying (drawing) in a linear manner.
- the shape of the coating film made of the metal bonding composition in the state of being applied and before being fired by heating can be made into a desired shape. Therefore, the metal bonding material (silver particle sintered layer) 12 after sintering by heating may be either planar or linear, and may be discontinuous even if it is continuous on the first body to be bonded. It may be.
- composition for metal bonding for example, screen printing (metal mask printing), dispenser method, pin transfer method, dipping, spray method, bar coat method, spin coat method, ink jet method, brush application method It may be appropriately selected from a casting method, a flexo method, a gravure method, an offset method, a transfer method, a hydrophilic / hydrophobic pattern method, a syringe method and the like.
- the viscosity of the composition for metal bonding is, for example, preferably in the range of 0.01 to 5000 Pa ⁇ S, more preferably in the range of 0.1 to 1000 Pa ⁇ S, and still more preferably in the range of 1 to 100 Pa ⁇ S. .
- a wide method can be applied as a method of apply
- the viscosity can be adjusted by adjusting the particle size of silver particles, adjusting the content of the organic component, adjusting the compounding ratio of each component, adding a thickener, and the like.
- the viscosity of the metal bonding composition can be measured, for example, by a cone and plate viscometer (for example, a rheometer MCR301 manufactured by Anton Paar Co., Ltd.).
- coated is heat-dried.
- the metal bonding composition applied to the first object to be bonded usually has a large amount of organic component to secure the coatability (printability) and the pot life (pot life).
- the metal bonding composition is dried by heating in step (2) to reduce the content of the organic component in the metal bonding composition in advance. .
- the heating temperature (preliminary drying temperature) in the step (2) is preferably 25 ° C. or more and 100 ° C. or less. If the temperature is less than 25 ° C., the dispersion medium in the metal bonding composition can not be volatilized efficiently. When the temperature exceeds 100 ° C., the dispersion medium can be sufficiently volatilized, but a part of the dispersant attached to the silver particles may also volatilize, and sintering may start, in which case the second object When the bonded body is pressed, it can not be brought into close contact, and bonding without pressure becomes difficult.
- a more preferable lower limit of the predrying temperature is 50 ° C., and a further preferable lower limit is 60 ° C.
- the heating time in the said process (2) is not specifically limited, It is preferable to carry out until content of the organic component in the composition for metal joining does not change.
- the method of heating and drying in the step (2) is not particularly limited, and, for example, a conventionally known oven can be used.
- a 2nd to-be-joined body is pressed on the composition for metal bonding heat-dried.
- the second object to be bonded is preferably pressed with a load of 1 MPa or less.
- the pressing load is preferably 0.05 MPa or more. If the pressing load is less than 0.05 MPa, the adhesion is insufficient and there is a risk of peeling.
- the method of pressing the second bonded body in the step (3) is not particularly limited, and various conventionally known methods can be applied, but the composition for dried and heated metal bonding (dry film) It is preferable to apply a uniform pressure.
- Step (4) the metal bonding composition is heated and sintered to form a silver particle sintered layer.
- the dispersion medium is mainly volatilized out of the organic components, and the dispersant attached to the silver particles remains in the metal bonding composition, but the heating in the step (4) Most or all of the organic components in the metal bonding composition volatilize.
- the binder component is also sintered from the viewpoint of improving the strength of the bonding material and the bonding strength between members to be bonded, etc.
- the main purpose of the binder component is to adjust the viscosity of the metal bonding composition for application to various printing methods, and the binder condition may be controlled to remove all the binder component.
- the silver particle sintered layer preferably has a small residual amount of the organic component from the viewpoint of obtaining high bonding strength, and preferably contains substantially no organic component, but the organic component is preferably within a range that does not impair the effect of the present invention. It does not matter if part of the remains.
- the silver particles are not only bonded together in the metal bonding composition by heating in the step (4), but also in the vicinity of the interface between the first and second members to be bonded and the silver particle sintered layer. Then, the metal diffuses between adjacent layers. As a result, a strong bond is formed between the first bonding body and the silver particle sintered layer, and between the second bonding body and the silver particle sintered layer.
- the said process (4) may join while pressurizing a 1st to-be-joined body and a 2nd to-be-joined body, a 1st to-be-joined body and a 2nd to-be-joined body It may be joined under no pressure. Bonding under no pressure is excellent in productivity because pressing and heating are not performed simultaneously.
- the heating temperature in the step (4) is not particularly limited as long as it can form a silver particle sintered layer, but is preferably 200 to 300 ° C.
- the heating temperature is 200 to 300 ° C.
- organic components and the like can be removed by evaporation or decomposition while preventing damage to the first and second objects to be bonded, and high bonding strength can be obtained.
- temperature may be raised or lowered stepwise, and it is preferable to raise temperature from room temperature.
- the heating time in the step (4) is not particularly limited, and may be adjusted according to the heating temperature so that the bonding strength can be sufficiently obtained.
- the method of heating in step (4) is not particularly limited, and, for example, a conventionally known oven can be used.
- the heating in the step (4) may be performed in the air or in a nitrogen atmosphere.
- the silver particle sintered layer is preferably a dense sintered body from the viewpoint of obtaining a mechanically, electrically and thermally strong bonding state, and specifically, the porosity of the silver particle sintered layer Is preferably 20% by volume or less. According to the metal bonding composition of the present embodiment, it is possible to easily form a silver particle sintered layer having a porosity of 5 to 20% by volume even when bonding is performed under no pressure.
- the thickness of the silver particle sintered layer is, for example, 10 to 200 ⁇ m, more preferably 20 to 100 ⁇ m.
- the thickness of the silver particle sintered layer can be easily controlled by the thickness of the coating film.
- the application of the metal-bonded laminate according to the present embodiment is not particularly limited. However, when the metal-bonded laminate is a power semiconductor element (power device), it can be used for an electrical control device.
- An electrical control device comprising the metal-bonded laminate of the present invention is also an aspect of the present invention. Electrical control devices are used for electric control (switching of electric power) in the fields of on-vehicle, electric iron, industrial use, household use (home appliance), electric power (power generation) and the like.
- Example 1 While sufficiently stirring 2.0 g of 3-methoxypropylamine with a magnetic stirrer, 3.0 g of silver oxalate was added to thicken the solution. The obtained viscous substance was placed in a constant temperature bath and allowed to react, and then 10 g of levulinic acid was added to further react to obtain a suspension. Next, in order to replace the dispersion medium of the suspension, methanol was added and stirred, and then the nanosilver particles were precipitated and separated by centrifugation, and the supernatant was discarded. This operation was repeated once more. The amount of nano silver particles obtained was 2.1 g.
- nano silver particles and micron silver particles are mixed at a mass ratio of 7: 3, hexyl carbitol (dispersion medium) and ricinoleic acid (additive)
- a mixed solution of 9: 1) mixed at 9: 1 is added with stirring so that the mass ratio of the total amount of nanosilver particles and micron silver particles to the mixed solution is 9: 1, and mixed to obtain a metal bonding composition.
- Example 2 A metal bonding composition was produced in the same manner as in Example 1 except that the mixing ratio of nano silver particles to micron silver particles was changed to 8: 2.
- Example 3 A metal bonding composition was produced in the same manner as in Example 1 except that the mixing ratio of nano silver particles to micron silver particles was changed to 9: 1.
- Example 4 While sufficiently stirring 2.0 g of 3-methoxypropylamine with a magnetic stirrer, 3.0 g of silver oxalate was added to thicken the solution. The obtained viscous substance was placed in a constant temperature bath and allowed to react, and then 10 g of levulinic acid was added to further react to obtain a suspension. Next, in order to replace the dispersion medium of the suspension, methanol was added and stirred, and then the nanosilver particles were precipitated and separated by centrifugation, and the supernatant was discarded. This operation was repeated once more. The amount of nano silver particles obtained was 2.1 g.
- Nano silver particles were prepared by mixing the obtained nanosilver particles and submicron silver particles in a mass ratio of 5: 5, and mixing hexyl carbitol (dispersion medium) and ricinoleic acid (additive) at 9: 1. The mixture was added with stirring so that the mass ratio of the total of the submicron silver particles to the mixture was 9: 1, and mixed to obtain a metal bonding composition.
- Example 4 was carried out in the same manner as Example 4 except that the maximum temperature of firing was 250 ° C. in (1) tensile test and (2) preparation method of metal bonded laminate and measurement of bonding strength described later.
- Example 6 While sufficiently stirring 3.0 g of 3-methoxypropylamine with a magnetic stirrer, 3.0 g of silver oxalate was added to thicken the solution. The obtained viscous substance was placed in a constant temperature bath and allowed to react, and then 9 g of dodecylamine was added to further react to obtain a suspension. Next, in order to replace the dispersion medium of the suspension, methanol was added and stirred, and then the nanosilver particles were precipitated and separated by centrifugation, and the supernatant was discarded. This operation was repeated once more. The amount of nano silver particles obtained was 2.1 g.
- Nano silver particles were prepared by mixing the obtained nanosilver particles and submicron silver particles in a mass ratio of 4: 6 and mixing hexyl carbitol (dispersion medium) and ricinoleic acid (additive) at 9: 1. The mixture was added with stirring so that the mass ratio of the total of the submicron silver particles to the mixture was 9: 1, and mixed to obtain a metal bonding composition.
- Example 7 While sufficiently stirring 5.0 g of 3-methoxypropylamine with a magnetic stirrer, 3.0 g of silver oxalate was added to thicken the solution. The obtained viscous substance was placed in a thermostat and allowed to react to obtain a suspension. Next, in order to replace the dispersion medium of the suspension, methanol was added and stirred, and then the nanosilver particles were precipitated and separated by centrifugation, and the supernatant was discarded. This operation was repeated once more. The amount of nano silver particles obtained was 2.0 g. In addition, while sufficiently stirring 15.0 g of diglycolamine with a magnetic stirrer, 4.5 g of silver oxalate was added to thicken the solution.
- Nano silver particles were prepared by mixing the obtained nanosilver particles and submicron silver particles in a mass ratio of 4: 6 and mixing hexyl carbitol (dispersion medium) and ricinoleic acid (additive) at 9: 1.
- the mixture was added with stirring so that the mass ratio of the total of the submicron silver particles to the mixture was 9: 1, and mixed to obtain a metal bonding composition.
- the baking atmosphere flowed nitrogen and made oxygen concentration 300 ppm or less in (1) tension test mentioned later and (2) the preparation methods of a metal joining laminated body, and measurement of joint strength.
- Comparative Example 1 A metal bonding composition was prepared in the same manner as in Example 1 except that the mixing ratio of the nanosilver particles to the micron silver particles was changed to 6: 4.
- Comparative Example 2 A composition for metal bonding was produced in the same manner as in Example 1 except that Solsparse 54000 (manufactured by Nippon Lubrizol Corporation) was used instead of ricinoleic acid.
- the metal bonding composition was printed on a slide glass using a dumbbell-shaped No. 7-shaped metal mask (plate thickness 90 ⁇ m) defined in JIS K 6251.
- the printed metal bonding composition was placed in an oven set at 70 ° C. for 30 minutes to dry.
- a slide glass was placed on the dried composition for metal bonding, and placed in a reflow furnace (manufactured by Shin Apex Co., Ltd.) to perform baking treatment.
- the firing treatment in the reflow furnace was performed in the air, and the temperature was raised from room temperature to a maximum temperature of 275 ° C. at a heating rate of 3.8 ° C./min, and then held at 275 ° C. for 60 minutes. During the firing process, no pressure was applied and no pressure was applied.
- the fired composition for metal bonding was taken out from the reflow furnace, it was peeled off from the slide glass to obtain a test piece for tensile test.
- the tensile test was carried out at a measurement speed of 0.72 mm / min with an Instron universal tensile tester 5969.
- the tensile breaking stress and breaking elongation (strain) when the test piece broke were measured. Further, the slope in the range of 0.05 to 0.25% of strain in the obtained stress-strain curve (SS curve) was calculated from the approximate expression, and was used as the Young's modulus.
- the composition for metal joining was apply
- the applied metal bonding composition was placed in an oven set at 70 ° C. and dried for 30 minutes.
- a gold-sputtered Si chip (bottom area: 5 mm ⁇ 5 mm or 10 mm ⁇ 10 mm) was stacked on the dried metal bonding composition, and pressed at 0.2 MPa.
- the obtained laminated body was put into a reflow oven (made by Shin Apex company), and the baking process was performed.
- the firing treatment in the reflow furnace was performed in the air, and after raising the temperature from room temperature to a maximum temperature of 275 ° C. at a temperature rising rate of 3.8 ° C./min, the temperature was maintained at 275 ° C. for 60 minutes. During the firing process, no pressure was applied and no pressure was applied.
- a metal-bonded laminate was obtained in which a gold-sputtered Si chip was bonded onto a silver-plated DBC substrate by a metal bonding material comprising a sintered metal bonding composition.
- the bonding strength of the metal bonded laminate was measured using a bond tester (manufactured by Lesca) at normal temperature. As a test piece, what laminated
- the tensile breaking stress of the film when fired at 275 ° C. was 100 MPa or more, and the printability and the pot life were also excellent.
- all of the metal bonding laminates produced using such a composition for metal bonding have a measurement value of bonding strength of 40 MPa as the upper limit of measurement, and high bonding strength of 40 MPa or more.
- the tensile breaking stress of the film when fired at 275 ° C. is less than 100 MPa, and was produced using the composition for metal bonding of Comparative Examples 1 and 2.
- a heat cycle test was performed on the metal bonded laminate, and the void fraction increased significantly after the test, exceeding 40%. It is considered that this is because a crack occurred in the heat cycle test.
- the metal-joining laminated body produced using the composition for metal joining of the comparative example 2 had the void ratio after a test as high as 75%, and the joint strength was as low as 31 Mpa.
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Abstract
La présente invention concerne : une composition pour une liaison de métal, qui est appropriée pour la formation d'un matériau de liaison de métal qui fait preuve d'une excellente durabilité lorsqu'une charge thermique lui est appliquée pendant un essai de cycle thermique et similaire ; un stratifié de liaison de métal, la liaison de surfaces métalliques étant obtenue par cuisson de la composition pour une liaison de métal décrite ci-dessus ; et un dispositif de commande électrique. Selon la présente invention, la composition pour une liaison de métal est utilisée dans le but de lier des surfaces métalliques au moyen d'une cuisson ; et la composition pour une liaison de métal contient des particules d'argent et un milieu de dispersion. Les particules d'argent comprennent des nanoparticules qui possèdent des diamètres de particule de 1 à 99 nm, et des particules submicroniques, qui possèdent des diamètres de particule de 100 à 999 nm, et/ou des particules microniques, qui possèdent des diamètres de particule de 1 à 999 µm.Un film de la composition pour une liaison de métal cuit à 275 °C possède une contrainte de traction à la rupture supérieure ou égale à 100 MPa.
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JP2020164926A (ja) * | 2019-03-29 | 2020-10-08 | Dowaエレクトロニクス株式会社 | 接合用金属ペースト及びそれを用いた接合方法 |
JP2021038427A (ja) * | 2019-09-02 | 2021-03-11 | 株式会社大阪ソーダ | 銀粒子の焼結体 |
WO2021060126A1 (fr) * | 2019-09-25 | 2021-04-01 | Dowaエレクトロニクス株式会社 | Matériau de jonction, procédé de fabrication de matériau de jonction, procédé de jonction et dispositif semi-conducteur |
JP2021063274A (ja) * | 2019-10-15 | 2021-04-22 | 千住金属工業株式会社 | 接合材、接合材の製造方法及び接合体 |
JP2022016511A (ja) * | 2017-10-10 | 2022-01-21 | Dic株式会社 | オフセット印刷用銀微粒子インクの製造方法 |
WO2023106219A1 (fr) * | 2021-12-06 | 2023-06-15 | 株式会社ダイセル | Stratifié et élément de jonction |
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WO2023106219A1 (fr) * | 2021-12-06 | 2023-06-15 | 株式会社ダイセル | Stratifié et élément de jonction |
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TW201910458A (zh) | 2019-03-16 |
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