Paste composition, semiconductor device and method for manufacturing same, and electronic component and method for manufacturing same

Abstract

A paste composition containing silver particles (A) and a binder (B), in which the content of silver particles (A1) having a particle diameter of greater than 20 [mu] m is 5% by mass or less in 100% by mass of the silver particles (A), the content of the silver particles (A) is 95% by mass or more in 100% by mass of the total of the silver particles (A) and the binder (B), and the rate of change represented by formula (1) is 250% or more. Change rate = (S1-S0) / S0 * 100 (%) (1) [S0 is the crystallite size in the Miller index (111) of the silver particles in the dried product of the paste composition. And S1 is the crystallite size in the Miller index (111) of the silver particles in a treated product obtained by heating and pressurizing the dried product of the paste composition at 15 MPa and 200 DEG C for 2 minutes in a nitrogen atmosphere. ].

Description

Technical Field

[0001] This invention relates to ointment compositions, semiconductor devices and methods of manufacturing the same, and electronic components and methods of manufacturing the same. Background Technology

[0002] In recent years, there has been active development of power semiconductor devices using wide-bandgap semiconductor elements such as silicon carbide (SiC) and gallium nitride (GaN) with low power loss. In these power semiconductor devices, the wide-bandgap semiconductor elements are bonded to other components, such as semiconductor support components, through bonding members formed of bonding materials.

[0003] This wide-bandgap semiconductor device possesses inherent high heat resistance and the ability to operate at temperatures exceeding 250°C based on high current. This characteristic is achieved through the efficient dissipation of heat generated during operation by the device itself. Therefore, in addition to electrical and thermal conductivity, a bonding material with excellent long-term high-temperature resistance is also required.

[0004] The use of sintered materials as bonding materials is expanding. Sintered materials are paste compositions containing fine metal particles. These fine metal particles are sintered at a temperature significantly lower than the melting point of the metal itself, and after sintering, they can achieve thermal conductivity and heat resistance equivalent to that of bulk metals.

[0005] Sintered materials are classified into non-pressurized and pressurized types based on differences in the bonding process. Non-pressurized materials are heated but not pressurized during bonding. Pressurized materials are heated and pressurized simultaneously during bonding.

[0006] In fields requiring high connection reliability, such as automotive (vehicle inverters), pressurized types are used. The reason is that high connection reliability is achieved by forming a dense sintered body through pressure during bonding.

[0007] Traditional pressure-bonded materials typically heat to temperatures above 250°C during bonding, but this raises concerns about damage to surrounding components from high temperatures and reduced connection reliability due to residual stress caused by thermal expansion. Therefore, there is a need for pressure-bonded materials capable of low-temperature bonding.

[0008] For example, Patent Document 1 describes a technique that focuses on the change in microcrystal size before and after heat treatment and performs pressure bonding under low-temperature conditions with a bonding temperature of 200°C.

[0009] Existing technical documents

[0010] Patent documents

[0011] Patent Document 1: Japanese Patent Application Publication No. 2020-136580. Summary of the Invention

[0012] Methods for solving problems

[0013] The present invention relates to the following [1] to

[11] .

[0014] [1] A paste composition comprising silver particles (A) and a binder (B),

[0015] Of the 100% by mass of silver particles (A), the content of silver particles (Al) with a particle size greater than 20 μm is less than 5% by mass.

[0016] Of the total amount of silver particles (A) and binder (B) in 100% by mass, the content of silver particles (A) is 95% by mass or more.

[0017] The rate of change expressed by the following formula (1) is more than 250%.

[0018] Rate of change = (S1-S0) / S0×100(%)(1).

[0019] [S0 is the microcrystal size in Miller index (111) of the silver particles in the dried product of the ointment composition.]

[0020] S1 is the microcrystal size in the Miller index (111) of silver particles in a treated product obtained by heating and pressurizing a dried product of the ointment composition at 15 MPa and 200°C for 2 minutes under nitrogen environment.

[0021] [2] The ointment composition as described in [1] above, wherein the content of silver particles (A2) with a particle size of 1.0 to 20 μm in 100% by mass of silver particles (A) is 50% by mass or less.

[0022] [3] The ointment composition as described in [1] or [2] above, wherein the content of silver particles (A3) with a particle size of less than 1.0 μm in 100% by mass of silver particles (A) is 50% by mass or more.

[0023] [4] The ointment composition as described in any one of [1] to [3] above, wherein the specific surface area of ​​the silver particles (A) is 1.4 m². 2 / g or more.

[0024] [5] The paste composition as described in any one of [1] to [4] above, wherein the adhesive (B) comprises one or more selected from thermosetting resins and thermoplastic resins.

[0025] [6] The paste composition as described in any one of [1] to [5] above, wherein the 5% mass weight reduction temperature of the adhesive (B) is above 250°C.

[0026] [7] The ointment composition as described in any one of [1] to [6] above, wherein,

[0027] The ointment composition contains a solvent (C),

[0028] Of the total amount of silver particles (A), adhesive (B), and solvent (C) in 100% by mass, the content of solvent (C) is 10-30% by mass.

[0029] [8] A semiconductor device, wherein the semiconductor device has a junction formed by any one of the paste compositions described in [1] to [7].

[0030] [9] A method for manufacturing a semiconductor device, wherein the method comprises:

[0031] The process of applying the paste composition described in any one of [1] to [7] above to the semiconductor support component;

[0032] The process of mounting the semiconductor element onto the paste composition; and

[0033] The process of heating and pressurizing the semiconductor element and the semiconductor support component to bond them together.

[0034] The heating and pressurizing bonding conditions are carried out at 180–300°C and 1–30 MPa for 0.5–10 minutes.

[0035]

[10] An electronic component having a joint formed from the paste composition described in any one of [1] to [7] above.

[0036]

[11] A method for manufacturing an electronic component, wherein the method comprises a step of forming a joint from the paste composition described in any one of [1] to [7] above. Detailed Implementation

[0037] For the bonding method described in Patent Document 1, the threshold of the bond strength, which serves as the evaluation criterion for sinterability, is 20 MPa, making it difficult to say that it has sufficient bonding strength.

[0038] The purpose of this invention is to provide a paste composition with high coatability, high bonding strength achieved by heating and pressurizing under low temperature conditions, and capable of bonding that is difficult to peel off due to thermal cycling, as well as a semiconductor device using the paste composition and a method for manufacturing the same, and an electronic component and a method for manufacturing the same.

[0039] The inventors have focused on the change in the microcrystal size of silver particles during heating and pressurization, and have discovered that by selecting silver particles with good sinterability in the pressurization process, it is possible to provide a paste composition with high coatability, high bonding strength through heating and pressurization under low temperature conditions, and a bond that is difficult to peel off due to thermal cycling, as well as a semiconductor device and a method for manufacturing the same using the paste composition, and an electronic component and a method for manufacturing the same.

[0040] According to the present invention, a paste composition with high coatability, high adhesive strength achieved by heating and pressurizing under low temperature conditions, and capable of bonding that is difficult to peel off due to thermal cycling, as well as a semiconductor device using the paste composition and a method for manufacturing the same, and an electronic component and a method for manufacturing the same.

[0041] The embodiments of the present invention will be described in detail below.

[0042] In the following description, the description of the numerical range "A~B" means "above A and below B" including the endpoint. When it is described as "can be A~B, can be C~D, or can be E~F", the upper and lower limits can be arbitrarily combined. In addition, the upper or lower limit of the numerical range described in this specification can also be replaced by the values ​​shown in the embodiments.

[0043] [Ointment Composition]

[0044] The ointment composition of the present invention comprises silver particles (A) and binder (B), wherein the content of silver particles (A1) with a particle size greater than 20 μm is 5% by mass or less in 100% by mass of the silver particles (A) and the content of silver particles (A) is 95% by mass or more in 100% by mass of the total amount of the silver particles (A) and the binder (B), and the rate of change expressed by the following formula (1) is 250% or more.

[0045] Rate of change = (S1 - S0) / S0 × 100 (%) (1)

[0046] Here, S0 is the microcrystal size in Miller index (111) of the silver particles in the dried product of the ointment composition.

[0047] S1 is the microcrystal size in Miller index (111) of silver particles in a treated product obtained by heating and pressurizing the dried product of the ointment composition at 15 MPa and 200 °C for 2 minutes under nitrogen environment.

[0048] The paste composition of the present invention has good spreadability, can be pressure bonded under low temperature conditions, and has high adhesive strength.

[0049] The details of the reasons are still unclear, but the following is speculation.

[0050] That is, crystal growth occurs within the particles and through sintering between them. It is believed that the greater the degree of crystal growth, the more efficient the sintering. Generally, the smaller the microcrystal size, the easier the crystal growth; the degree of crystal growth is considered to vary depending on the particle shape, size, and processing conditions. In silver particles where the rate of change in microcrystal size is assumed to be large due to the bonding process (heating and pressurizing at 15 MPa and 200°C for 2 minutes in a nitrogen environment), the silver particles are tightly packed together under these conditions, resulting in a high contact frequency, thus sintering is easier. Specifically, if the rate of change of silver particle (A) {((S1-S0) / S0)×100} is greater than 250%, good sinterability can be achieved during low-temperature heating and pressurization.

[0051] Furthermore, as described above, silver particles (A) exhibit excellent sintering properties during heating and pressurization at low temperatures, resulting in high bonding performance. Therefore, the content of the binder (B) required for bonding can be reduced. Specifically, in the paste composition of the present invention, the content of silver particles (A) is 95% by mass or more out of 100% by mass of the total amount of silver particles (A) and binder (B). Thus, because the paste composition of the present invention contains a high content of silver particles (A), a bond with not only high bonding strength but also high thermal conductivity and electrical conductivity can be formed.

[0052] <Silver Particles (A)>

[0053] The rate of change of the silver particles (A) expressed by the following formula (1) is more than 250%.

[0054] Rate of change = (S1 - S0) / S0 × 100 (%) (1)

[0055] Here, S0 is the crystallite size in Miller index (111) of the silver particles in the dried product of the ointment composition. Additionally, S1 is the crystallite size in Miller index (111) of the silver particles in the treated product obtained by heating and pressurizing the dried product of the ointment composition at 15 MPa and 200°C for 2 minutes under nitrogen conditions.

[0056] If the rate of change {((S1-S0) / S0)×100} is 250% or higher, a paste composition can be obtained that exhibits high adhesive strength and is resistant to peeling caused by thermal cycling through heating and pressure bonding under low-temperature conditions. Furthermore, there is no particular upper limit to the rate of change {((S1-S0) / S0)×100}, and from the viewpoint of reducing structural changes in the sintered layer caused by thermal cycling after bonding, it can be 500% or lower.

[0057] From this perspective, the rate of change {((S1-S0) / S0)×100} can be 255-475%, 270-450%, 285-425%, or 300-400%.

[0058] The crystallite size S0 of the silver particles (A) can also be 30 nm to 70 nm. If it is within the above range, crystals are easily grown under heating and pressure, and therefore sintering is easy to perform.

[0059] From this perspective, the microcrystal size S0 can also be 40nm to 60nm.

[0060] The crystallite size S0 can be determined as follows: Silver particles (A) in the dried paste composition are compacted to form a cake. This cake is coated onto glass, and using an X-ray diffraction apparatus, the crystallite size S0 can be calculated from the peaks on the Miller index (111) plane using a focusing method with CuKα rays as the radiation source, according to the Scherrer formula. Specifically, it can be obtained by the method described in the examples.

[0061] The crystallite size S1 of the silver particles (A) can also be 105–420 nm. If it is 105 nm or larger, the structural changes of the sintered layer after bonding can be reduced. If it is 420 nm or smaller, the stress generated inside the sintered layer can be reduced.

[0062] From this perspective, the microcrystal size S1 can be 120–400 nm, 130–350 nm, or 140–300 nm.

[0063] The microcrystal size S1 can be determined as follows: Silver particles (A) in the dried paste composition are compacted to form a cake. Under a nitrogen environment, the cake is heated to 200°C at a heating rate of 60°C / min while applying a pressure of 15 MPa. After heating and pressurizing at 15 MPa and 200°C for 2 minutes, it is cooled to room temperature (25°C) at a cooling rate of 110°C / min to obtain a sintered body. The powder is obtained by pulverizing the sintered body in a mortar. The powder is coated on glass, and the microcrystal size S1 can be calculated using an X-ray diffraction apparatus with CuKα rays as the radiation source, based on the Scherrer formula, targeting the peaks on the Miller index (111) plane. Specifically, it can be obtained by the method described in the examples.

[0064] By making the particle size of silver particles (A) within the range described later, and making the microcrystalline particle size S0 of silver particles (A) within the range described later, there is a tendency to increase the rate of change {((S1-S0) / S0)×100}.

[0065] It should be noted that the rate of change of the silver particles {((S1-S0) / S0)×100} can be easily measured using the aforementioned methods for measuring S0 and S1.

[0066] The average particle size of the silver particles (A) can also be 0.62 to 5.0 μm. If it is 0.62 μm or larger, the contact frequency between the silver particles increases during pressurization, thus improving sinterability. If it is 5.0 μm or smaller, damage to the semiconductor device or substrate during pressurization can be reduced. In addition, if the average particle size of the silver particles (A) is 0.62 to 5.0 μm, it tends to have a higher rate of change {((S1-S0) / S0)×100}.

[0067] From this perspective, the average particle size of the silver particles (A) can be 0.65 to 3.0 μm, less than 2.0 μm, or less than 1.75 μm.

[0068] The shape of silver particles (A) is not particularly limited; for example, they can be spherical or flake-shaped. Silver particles (A) can also be spherical. Silver particles (A) can be primary particles or secondary particles formed by the aggregation of primary particles.

[0069] Furthermore, the silver particle (A) can be either hollow or solid; from the perspective of low-temperature sintering, it can be a hollow particle. Here, a hollow particle refers to a particle with voids inside. When the silver particle (A) is hollow, voids can exist in the center of the silver particle. Conversely, a solid particle refers to a particle with no substantial space inside.

[0070] The specific surface area of ​​silver particles (A) calculated using the BET method can also be 1.4 m². 2 / g or more. If the specific surface area is 1.4m² 2 A specific surface area of ​​2.0 m² or higher can increase the contact between silver particles and also increase the proportion of highly reactive silver atoms on the particle surface. Furthermore, this specific surface area can also be 2.0 m². 2 / g or less. If the specific surface area is 2.0m² 2 When the concentration is below / g, the viscosity of the paste composition can be reduced, and the aggregation of silver particles can be decreased.

[0071] From this perspective, the specific surface area could also be 1.5–1.95 m². 2 / g.

[0072] The specific surface area of ​​silver particles (A) can be determined using a specific surface area measuring device and by the BET single-point method based on nitrogen adsorption, specifically by the method described in the examples.

[0073] Of the total amount of silver particles (A) and adhesive (B) 100% by mass, the content of silver particles (A) is 95% by mass or more. If this content is 95% by mass or more, a paste composition with high adhesive strength and capable of bonding by heating and pressurizing under low-temperature conditions and resisting peeling caused by thermal cycling can be obtained.

[0074] Furthermore, in the total amount of silver particles (A) and binder (B) of 100% by mass, the content of silver particles (A) can also be 99% by mass or less. If this content is 99% by mass or less, the function of binder (B) is fully utilized, and a paste composition with high coatability and the ability to reduce structural changes in the sintered layer caused by thermal runaway after bonding can be obtained.

[0075] From this perspective, the content can be 95-99% by mass, 95.5-98.7% by mass, or 96-98.5% by mass.

[0076] From the point of view of sinterability, the total amount of metals present in the paste composition, in which the silver content is 100% by mass, can be 60% by mass or more, 80% by mass or more, 90% by mass or more, 95% by mass or more, or 99% by mass or more, or it can contain no metals other than silver.

[0077] <<Silver Particles (A1)>>

[0078] In the silver particles (A) of the present invention, the content of silver particles (Al) with a particle size greater than 20 μm is 5% by mass or less in 100% by mass. The content of these silver particles (Al) can also be 0% by mass.

[0079] If the content is 5% by mass or less, no scraper marks will remain during printing and coating, and the pressure load can be applied evenly to the bonding layer. Therefore, if the content is 5% by mass or less, a paste composition with high coatability, high adhesive strength due to heating and pressure bonding under low temperature conditions, and the ability to achieve a bond that is difficult to peel off due to thermal cycling can be obtained.

[0080] From this perspective, the content can be less than 2.5% by mass, less than 1.5% by mass, or less than 1.0% by mass.

[0081] <<Silver Particles (A2)>>

[0082] In the silver particles (A) of the present invention, the content of silver particles (A2) with a particle size of 1.0 to 20 μm in 100% by mass can also be less than 50% by mass.

[0083] If the content is less than 50% by mass, a uniform silver sintered layer can be formed. Alternatively, the content can be 5% by mass or more. If the content is 5% by mass or more, the contact frequency between silver particles can be increased.

[0084] From this perspective, the content can be 8–45% by mass, 10–40% by mass, or 15–36% by mass.

[0085] <<Silver Particles (A3)>>

[0086] In the silver particles (A) of the present invention, the content of silver particles (A3) with a particle size of less than 1.0 μm in 100% by mass can also be more than 50% by mass.

[0087] If the content is 50% by mass or more, a uniform silver sintered layer can be formed. Alternatively, the content can be 95% by mass or less. If the content is 95% by mass or less, the contact frequency between silver particles can be increased.

[0088] From this perspective, the content can be 55–92% by mass, 60–90% by mass, or 64–85% by mass.

[0089] (Method for manufacturing silver particles (A))

[0090] The method for manufacturing silver particles (A) includes a step of adding ammonia to an aqueous solution containing a silver compound to obtain a silver ammonia complex solution; and a step of reducing the silver ammonia complex in the silver ammonia complex solution obtained in the step with a reducing compound to obtain a slurry containing silver particles.

[0091] (Process for obtaining silver ammonia complex solution)

[0092] In this process, ammonia is added to an aqueous solution containing silver compounds to obtain a silver-ammonia complex solution.

[0093] Examples of silver compounds include silver nitrate, silver chloride, silver acetate, silver oxalate, and silver oxide. From the perspective of solubility in water, silver compounds can also be silver nitrate or silver acetate.

[0094] The amount of ammonia added relative to 1 mol of silver in an aqueous solution containing silver compounds can be 2–50 mol, or more than 5 mol, or more than 10 mol. If the amount of ammonia added is within the above range, the average particle size of the primary particles can be set within the above range.

[0095] (Process for obtaining a slurry containing silver particles)

[0096] In this process, the silver ammonia complex in the silver ammonia complex solution obtained in the previous process is reduced with a reducing compound to obtain a slurry containing silver particles.

[0097] By reducing the silver ammonia complex with a reducing compound, the primary particles of silver in the silver ammonia complex condense to form secondary particles (hollow particles) with voids in the center.

[0098] By appropriately adjusting the amount of silver and the content of reducing compounds in the silver ammonia complex, the aggregation of the primary particles can be controlled, and the average particle size of the resulting secondary particles can be set within the aforementioned range.

[0099] There are no particular limitations on reducing compounds, as long as they possess the reducing power to reduce silver ammonia complexes and cause silver precipitation. Examples of reducing compounds include, for instance, hydrazine derivatives. Examples of hydrazine derivatives include hydrazine monohydrate, methylhydrazine, ethylhydrazine, n-propylhydrazine, isopropylhydrazine, n-butylhydrazine, isobutylhydrazine, sec-butylhydrazine, tert-butylhydrazine, n-pentylhydrazine, isopentylhydrazine, neopentylhydrazine, tert-pentylhydrazine, n-hexylhydrazine, isohexylhydrazine, n-heptylhydrazine, n-octylhydrazine, n-nonylhydrazine, n-decylhydrazine, n-undecylhydrazine, n-dodecylhydrazine, cyclohexylhydrazine, phenylhydrazine, 4-methylphenylhydrazine, benzylhydrazine, 2-phenylethylhydrazine, 2-hydrazinoethanol, acetylhydrazine, etc. These can be used alone or in combination of two or more.

[0100] For every 1 mol of silver in the silver-ammonia complex, the content of the reducing compound can be 0.25–20.0 mol, less than 10.0 mol, or less than 5.0 mol. If the content of the reducing compound is within the above range, the average particle size of the resulting secondary particles can be set within the above range.

[0101] Furthermore, the temperature of the silver ammonia complex solution during the reduction of the silver ammonia complex can be less than 30°C or between 0 and 20°C. If the temperature of the silver ammonia complex solution is within this range, the aggregation of the primary particles can be controlled, and the average particle size of the resulting secondary particles can be set within the aforementioned range.

[0102] <Adhesive (B)>

[0103] The adhesive (B) may contain one or more selected from thermosetting resins and thermoplastic resins.

[0104] <<Thermosetting Resins>>

[0105] As a thermosetting resin, any thermosetting resin generally used as an adhesive can be used without particular limitation. The aforementioned thermosetting resin can be a liquid resin at room temperature (25°C) or a resin that becomes a paste by dilution in a solvent or the like. As a thermosetting resin, it is acceptable to include at least one selected from cyanate ester resins, epoxy resins, acrylic resins, and maleimide resins. These can be used alone or in combination of two or more.

[0106] Cyanate ester resins are compounds containing -NCO groups within their molecules, and are resins produced by reacting these -NCO groups upon heating. Specific examples include 1,3-dicyanophenyl, 1,4-dicyanophenyl, 1,3,5-tricyanophenyl, 1,3-dicyanonaphthalene, 1,4-dicyanonaphthalene, 1,6-dicyanonaphthalene, 1,8-dicyanonaphthalene, 2,6-dicyanonaphthalene, 2,7-dicyanonaphthalene, 1,3,6-tricyanonaphthalene, 4,4'-dicyanobiphenyl, bis(4-cyanophenyl)methane, and bis(3,5-dimethyl... Examples of polyfunctional cyanate ester resins include 2,2-bis(4-cyanophenyl)methane, 2,2-bis(3,5-dibromo-4-cyanophenyl)propane, bis(4-cyanophenyl) ether, bis(4-cyanophenyl) sulfide, bis(4-cyanophenyl) sulfone, tris(4-cyanophenyl) phosphite, tris(4-cyanophenyl) phosphate, and cyanate esters obtained by reacting phenolic varnish resins with cyanide halides. Additionally, prepolymers with triazine rings formed by trimerizing the cyanate groups of these polyfunctional cyanate ester resins can also be used. These prepolymers can be obtained by polymerizing the aforementioned polyfunctional cyanate ester resin monomers using, for example, acids such as inorganic acids and Lewis acids, bases such as sodium alkoxides and tertiary amines, and salts such as sodium carbonate as catalysts.

[0107] As a curing accelerator for cyanate ester resins, commonly known curing accelerators can be used. Examples include organometallic complexes such as zinc octoate, tin octoate, cobalt naphthenate, zinc naphthenate, and iron acetylacetonate; metal salts such as aluminum chloride, tin chloride, and zinc chloride; and amines such as triethylamine and dimethylbenzylamine, but these are not limited to. One or more of these curing accelerators can be used.

[0108] Epoxy resins are compounds having one or more glycidyl groups within their molecules, and are resins formed by reacting the glycidyl groups through heating. The aforementioned epoxy resins can also be compounds containing two or more glycidyl groups in one molecule. Examples include, but are not limited to, difunctional compounds formed by epoxidation of bisphenol compounds such as bisphenol A, bisphenol F, and biphenol, or their derivatives; hydrogenated bisphenol A, hydrogenated bisphenol F, hydrogenated biphenol; diols with alicyclic structures such as cyclohexanediol, cyclohexanediethanol, and cyclohexanediethanol; aliphatic diols such as butanediol, hexanediol, octanediol, nonanediol, and decanediol; trifunctional compounds formed by epoxidation of compounds having a trihydroxyphenylmethane skeleton or an aminophenol skeleton; and polyfunctional compounds formed by epoxidation of phenol-formaldehyde varnish resins, cresol-formaldehyde varnish resins, phenol aralkyl resins, biphenyl aralkyl resins, naphthol aralkyl resins, and polybutadiene. Furthermore, the aforementioned epoxy resin can be a liquid epoxy resin, either alone or as a mixture, at room temperature (25°C). It is a compound containing one glycidyl group per molecule and can also be used as a reactive diluent as commonly used. Examples of reactive diluents include monofunctional aromatic glycidyl ethers such as phenyl glycidyl ether and tolyl glycidyl ether, as well as aliphatic glycidyl ethers.

[0109] Examples of curing agents for epoxy resins include aliphatic amines, aromatic amines, dicyandiamide, dihydrazide compounds, acid anhydrides, phenolic resins, and organic peroxides.

[0110] Examples of diacylhydrazides include adipic acid diacylhydrazide, dodecanoic acid diacylhydrazide, isophthalic acid diacylhydrazide, and carboxylic acid diacylhydrazide.

[0111] Examples of acid anhydrides include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylenetetrahydrophthalic anhydride, dodecenylsuccinic anhydride, reactants of maleic anhydride and polybutadiene, and copolymers of maleic anhydride and styrene.

[0112] Examples of organic peroxides include hydroperoxides, dialkyl peroxides, dicumyl peroxides, benzoyl peroxides, lauroyl peroxides, acetyl peroxides, acyl peroxides, as well as peroxide ketals such as cumene peroxide, 1,1-di-tert-butylperoxycyclohexane peroxide, peroxide esters such as tert-butylperoxybenzoate, and further, so-called room-temperature curing organic peroxides, such as methyl ethyl ketone peroxide.

[0113] Furthermore, it can be combined with a curing accelerator to promote curing. Examples of curing accelerators for epoxy resins include imidazoles, triphenylphosphine or tetraphenylphosphine and their salts, amine compounds such as diazabicycloundecene and their salts, etc. Curing accelerators can also be 2-methylimidazole, 2-ethylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-C 11 H 23 Imidazole compounds, such as the addition products of 2-methylimidazole and 2,4-diamino-6-vinyltriazine, are also possible. They can also be imidazole compounds with a melting point above 180°C.

[0114] Examples of acrylic resins include, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 1,2-cyclohexanediol mono(meth)acrylate, 1,3-cyclohexanediol mono(meth)acrylate, 1,4-cyclohexanediol mono(meth)acrylate, 1,2-cyclohexanediethanol mono(meth)acrylate, 1,3-cyclohexanediethanol mono(meth)acrylate, 1,4-cyclohexanediethanol mono(meth)acrylate, 1,2-cyclohexanediethanol mono(meth)acrylate, 1,3-cyclohexanediethanol mono(meth)acrylate, 1,4-cyclohexanediethanol mono(meth)acrylate, 1,2-cyclohexanediol mono(meth)acrylate. Diethanol mono(meth)acrylate, 1,3-cyclohexanediethanol mono(meth)acrylate, 1,4-cyclohexanediethanol mono(meth)acrylate, glycerol mono(meth)acrylate, glycerol di(meth)acrylate, trimethylolpropane mono(meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol mono(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, neopentyl glycol mono(meth)acrylate, and other hydroxyl-containing (meth)acrylates, as well as carboxyl-containing (meth)acrylates obtained by reacting these hydroxyl-containing (meth)acrylates with dicarboxylic acids or their derivatives. Examples of dicarboxylic acids that can be used here include, for example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, octanoic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, and their derivatives.

[0115] In addition, examples of acrylic resins include polyethers, polyesters, polycarbonates, poly(meth)acrylates with molecular weights of 100 to 10,000 and compounds having (meth)acryloyl groups; (meth)acrylates having hydroxyl groups; and (meth)acrylamides having hydroxyl groups.

[0116] Maleimide resins are compounds containing one or more maleimide groups within a single molecule, and are resins obtained by reacting the maleimide groups through heating. Examples of maleimide resins include N,N'-(4,4'-diphenylmethane)bismaleimide, bis(3-ethyl-5-methyl-4-maleimidephenyl)methane, and 2,2-bis[4-(4-maleimidephenoxy)phenyl]propane. Maleimide resins can also be compounds obtained by reacting a dimeric acid diamine with maleic anhydride; or compounds obtained by reacting maleimide-modified amino acids such as maleimideacetic acid or maleimidehexanoic acid with polyols. The aforementioned maleimide-modified amino acids can be obtained by reacting maleic anhydride with aminoacetic acid or aminohexanoic acid. The aforementioned polyols can be polyether polyols, polyester polyols, polycarbonate polyols, poly(meth)acrylate polyols, or polyols that do not contain aromatic rings.

[0117] <<Thermoplastic Resins>>

[0118] As a thermoplastic resin, any thermoplastic resin generally used as an adhesive can be used without particular limitation. Examples include acrylic resins, methacrylic resins, vinyl resins, carbonate resins, cellulose, polyolefin resins, ethylene-vinyl acetate copolymers, and polyamide resins. It is acceptable as long as at least one of the thermoplastic resins selected from the examples is included. These can be used alone or in combination of two or more.

[0119] Of the total amount of silver particles (A) and binder (B) in 100% by mass, the content of binder (B) is 5.0% by mass or less. If this content is 5.0% by mass or less, it is possible to fill the voids in the structure formed by silver sintering without hindering the sintering of silver particles.

[0120] Of the total amount of silver particles (A) and binder (B) being 100% by mass, the content of binder (B) may also be 0.1% by mass or more. If this content is 0.1% by mass or more, the stress applied to the sintered layer can be mitigated by filling the voids in the structure formed by silver sintering with resin.

[0121] From this perspective, the content can be 0.1–5.0% by mass, 0.5–4.8% by mass, 1.0–4.5% by mass, or 1.5–4.0% by mass.

[0122] <<Physical Properties, etc.>>

[0123] The 5% weight reduction temperature of the adhesive (B) can also be 250°C or higher. If it is 250°C or higher, the thermal decomposition of the resin during bonding can be reduced. Furthermore, there is no particular limitation on the upper limit of the 5% weight reduction temperature of the adhesive (B), and from the viewpoint of adhesive availability, compatibility with solvents, etc., it can also be 450°C or lower.

[0124] From this perspective, the 5% mass weight reduction temperature of the adhesive (B) can be 250–450°C, 300–425°C, or 350–400°C.

[0125] The 5% weight reduction temperature of adhesive (B) can be determined by differential thermal and thermogravimetric analysis (TGA) apparatus, specifically by the method described in the examples.

[0126] <Solvent (C)>

[0127] From an operational point of view, the ointment composition of the present invention may also contain a solvent (C).

[0128] Examples of solvents (C) include butyl carbitol, acetic acid cellosolve, ethyl cellosolve, butyl cellosolve, butyl cellosolve acetate, butyl carbitol acetate, diethylene glycol dimethyl ether, diacetone alcohol, N-methyl-2-pyrrolidone (NMP), dimethylformamide, N,N-dimethylacetamide (DMAc), γ-butyrolactone, 1,3-dimethyl-2-imidazolinone, 3,5-dimethyl-1-adamantaneamine (DMA), and dihydroterpinyloxyethanol, among other terpene ethers. These can be used alone or in combination of two or more.

[0129] When the ointment composition of the present invention contains solvent (C), the content of solvent (C) in 100% by mass of the ointment composition can also be 5% to 50% by mass. When the content is 5% by mass or more, good spreadability can be imparted. When the content is 50% by mass or less, the sedimentation of silver particles during standing of the ointment composition can be reduced, and the usable time can be increased.

[0130] From this perspective, the content can be 10–40% by mass, 12–30% by mass, or 15–25% by mass.

[0131] When the ointment composition of the present invention contains a solvent (C), the content of the solvent (C) may be 10 to 30% by mass in 100% by mass of the total amount of the silver particles (A), the binder (B), and the solvent (C).

[0132] When the content is 10% by mass or more, it imparts good coatability. When the content is 30% by mass or less, it reduces the sedimentation of silver particles during the settling of the paste composition, thus increasing the pot life.

[0133] From this perspective, the content could also be 12–25% by mass.

[0134] <Other Ingredients>

[0135] In addition to the above-mentioned components, the paste composition of the present invention may also include, as needed, low-stress agents such as rubber and silicone; coupling agents; defoamers; surfactants; colorants such as pigments and dyes; various polymerization inhibitors; antioxidants; solvents; fluxes; and other additives commonly used in such compositions. Any one of these additives may be used, or two or more may be used in combination.

[0136] The ointment composition of the present invention may contain a resin with an aromatic amine skeleton or may not contain a resin with an aromatic amine skeleton.

[0137] The total content of silver particles (A), binder (B) and solvent (C) in the ointment composition of the present invention can be 80-100% by mass, 90-99.95% by mass, or 95-99.9% by mass.

[0138] The total content of silver particles (A) and binder (B) in the 100% by weight of the solid components of the paste composition of the present invention can be 80-100% by weight, 90-100% by weight, or 95-99.9% by weight.

[0139] Here, solid components refer to the components remaining after removing the solvent (C) from the ointment composition.

[0140] The silver particles (A), binder (B), solvent (C) as needed, and various additives are thoroughly mixed, and then the mixture is kneaded using a disperser, kneader, three-roll mill, etc., and then degassed to prepare the paste composition of the present invention.

[0141] <Physical properties of the ointment composition, etc.>

[0142] (Viscosity)

[0143] From the viewpoint of coatability, the viscosity of the paste composition of the present invention can be 1 to 200 Pa·s, 10 to 100 Pa·s, 12 to 50 Pa·s, or 15 to 25 Pa·s.

[0144] The viscosity values ​​mentioned above were measured using an E-type viscometer (3° cone) at 25°C and 2.0 rpm. Specifically, they can be measured using the methods described in the examples.

[0145] (Thixotropic index)

[0146] From the viewpoint of coatability, the thixotropic index of the ointment composition of the present invention can be 1 to 20, 2 to 10, or 3.5 to 7.

[0147] The thixotropic index mentioned above is the viscosity (V) measured using an E-type viscometer (3°) at a temperature of 25°C and a rotation speed of 2.0 rpm. 2.0 ) and viscosity (V) at 20 rpm 20 ), as their viscosity ratio (V 2.0 / V 20 Specifically, it can be determined using the methods described in the embodiments.

[0148] (shear strength)

[0149] The cured paste composition of the present invention can also have a shear strength of 80 MPa or more. When the shear strength is 80 MPa or more, the bonding strength is high and the bonding is difficult to peel off due to thermal cycling by heating and pressurizing under low temperature conditions.

[0150] From this perspective, the shear strength of the cured paste composition can be above 85 MPa, above 90 MPa, or above 92 MPa.

[0151] To determine the shear strength of the cured paste composition, the paste composition was applied to a copper frame, and a gold chip with a gold vapor-deposited layer was mounted on a 2mm × 2mm bonding surface. After curing at 200°C and 15MPa for 2 minutes, the thermal shear strength at 260°C was measured using a mounting strength measuring device. Specifically, the method described in the examples can be used for measurement.

[0152] (Volume resistivity)

[0153] The volume resistivity of the cured paste composition of the present invention can be 4.0 μΩ·cm or less. When the volume resistivity is 4.0 μΩ·cm or less, resistive heating in the joint can be reduced.

[0154] From this perspective, the volume resistivity of the cured paste composition can be below 3.5 μΩ·cm, below 3.4 μΩ·cm, or below 3.0 μΩ·cm.

[0155] Regarding the volume resistivity of the cured paste composition, the paste composition was coated onto a glass substrate with a thickness of 30 μm. After drying, the resistivity of the wiring obtained by curing at 200°C and 15 MPa for 2 minutes was measured using a resistivity meter via a four-terminal method. Specifically, the method described in the examples can be used for measurement.

[0156] Semiconductor devices and manufacturing methods thereof

[0157] The semiconductor device of the present invention has a bonding portion formed from the aforementioned paste composition. Because the semiconductor device of the present invention has a bonding portion formed from the aforementioned paste composition, it is possible to provide a semiconductor device for automotive components with good heat dissipation and connection reliability.

[0158] The semiconductor device may have semiconductor elements, a substrate, and a bonding portion for bonding these semiconductor elements to the substrate. The bonding portion is formed from the aforementioned paste composition.

[0159] The semiconductor device manufacturing method of the present invention is a method for manufacturing a semiconductor device having a semiconductor element and a semiconductor support member, comprising: a step of applying the aforementioned paste composition to the semiconductor support member; a step of mounting the semiconductor element to the paste composition; and a step of heating and pressurizing the semiconductor element and the semiconductor support member, wherein the heating and pressurizing bonding is performed at 180 to 300°C and 1 to 30 MPa for 0.5 to 10 minutes.

[0160] When the heating temperature in the heat-pressurized bonding process is above 180°C, sintering is fully carried out, and the bonding strength of the joint is improved. When the heating temperature is below 300°C, heat-induced degradation of components such as semiconductor elements and semiconductor support components is reduced.

[0161] From this perspective, the heating temperature can be 180–300℃, 185–250℃, or 190–210℃.

[0162] When the pressure during the heating and pressurizing process is above 1 MPa, sintering proceeds sufficiently, and the bonding strength of the joint is improved. When the pressure is below 30 MPa, the likelihood of damage to components such as semiconductor elements and semiconductor support parts due to pressure is reduced.

[0163] From this perspective, the pressure can be 1–30 MPa, 5–25 MPa, or 10–20 MPa.

[0164] Any known semiconductor device can be used, such as transistors and diodes. Furthermore, LEDs and other light-emitting devices can be cited as examples of such semiconductor devices. There are no particular limitations on the type of light-emitting device; for example, light-emitting devices formed by depositing nitride semiconductors such as InN, AlN, GaN, InGaN, AlGaN, and InGaAlN as a light-emitting layer on a substrate using methods such as MOCVD (metal-organic vapor deposition) can also be cited.

[0165] In addition, as semiconductor support components, examples include support components made of materials such as copper, copper-plated copper, PPF (pre-plated lead frame), glass epoxy, and ceramics.

[0166] By using the chip bonding material of this embodiment, semiconductor elements can also be bonded to substrates that have not undergone metal plating. The resulting semiconductor device exhibits improved connection reliability for post-installation temperature cycling compared to conventional methods. Furthermore, due to its sufficiently low resistance value and minimal change over time, it offers the advantage of minimal output degradation even during prolonged operation, resulting in a long lifespan.

[0167] [Electronic components and their manufacturing methods]

[0168] The electronic component of the present invention has a joint formed by the aforementioned paste composition. Because the electronic component of the present invention has a joint formed by the aforementioned paste composition, it is possible to provide an electronic component for automotive applications with good heat dissipation and reliable connection.

[0169] The electronic component may also have electronic elements, a substrate, and a bonding portion for bonding these electronic elements to the substrate. The bonding portion is formed from the aforementioned paste composition.

[0170] The method for manufacturing electronic components of the present invention is a method for manufacturing electronic components having a step of forming a joint from the aforementioned paste composition.

[0171] Example

[0172] The invention will then be described in detail with reference to embodiments, but the invention is not limited to these embodiments.

[0173] The substances shown in Table 1 and below were used as raw materials, etc.

[0174] (1) Silver particles

[0175] Table 1

[0176]

[0177] (2) Adhesive (resin)

[0178] ·jER1009 (Bisphenol A type solid epoxy resin, manufactured by Mitsubishi Chemical Corporation, molecular weight: 3800, 5% weight reduction temperature: 359°C).

[0179] JP-100 (Epoxy solid epoxy resin, manufactured by Nippon Soda Co., Ltd., molecular weight: 1300, 5% weight reduction temperature: 377°C).

[0180] (3) Solvent

[0181] ·TOE-100 (dihydroterpinyloxyethanol, manufactured by Nippon Terpene Chemical Co., Ltd., molecular weight: 198.31).

[0182] (4) Other ingredients

[0183] • Curing agent: PERCUMYL D (dicumyl peroxide, manufactured by Nippon Oil Co., Ltd., molecular weight 270.37).

[0184] • Flux: KE-604 (trade name "Pine Crystal KE-604", hydride of acrylic acid modified rosin, manufactured by Arakawa Chemical Industry Co., Ltd.).

[0185] [Examples 1-7 and Comparative Examples 1-10]

[0186] Mix the ingredients according to the proportions shown in Table 2, and knead them with a roller to obtain a paste composition.

[0187] The resulting ointment composition was evaluated as described below. The results are shown in Table 2.

[0188] [evaluate]

[0189] (1) Microcrystalline particle sizes S0, S1 and their rate of change {((S1-S0) / S0)×100}

[0190] The obtained paste composition was dried at 80°C for 30 minutes to obtain a cake-like substance.

[0191] The cake-shaped material was coated on glass with a thickness of 200 μm. Using an X-ray diffraction apparatus (product name: SmartLab SE, manufactured by Rigaku Corporation), the crystallite size S0 (nm) was calculated based on the Scherrer formula for the peak of the Miller index (111) plane using the focusing method with CuKα rays as the X-ray source.

[0192] It should be noted that the fitting function used was a segmented quasi-Voigt function, the width was FWHD, and the Scherrer constant was 0.94.

[0193] In addition, under a nitrogen environment, the cake was heated to 200°C at a rate of 60°C / min while applying a pressure of 15 MPa. After being heated and pressurized at 15 MPa and 200°C for 2 minutes, it was cooled to room temperature (25°C) at a rate of 110°C / min to obtain a sintered body. The sintered body was then pulverized in a mortar to obtain powder. The powder was coated onto glass, and the crystallite size S1 (nm) was calculated using a concentrated method with CuKα rays as the radiation source, based on the Scherrer formula, targeting the Miller index (111) peak.

[0194] It should be noted that the fitting function used was the segmented Voigt fitting function, the width was FWHD, and the Scherrer constant was 0.94.

[0195] Furthermore, the rate of change {((S1-S0) / S0)×100} (%) is calculated from the above S0 and S1.

[0196] (2) Viscosity

[0197] The viscosity of the obtained paste composition was measured using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd., product name: VISCOMETER-TV22, using a conical rotor: 3°×R14) (3° cone). The viscosity was measured at a temperature of 25°C and a rotation speed of 2.0 rpm.

[0198] (3) Thixotropic index

[0199] Using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd., product name: VISCOMETER-TV22, with a conical rotor: 3°×R14), the viscosity (Vt) of the obtained paste composition was measured at 25°C and 2.0 rpm. 2.0 ) and viscosity (V) at 20 rpm 20 Viscosity V 2.0 Relative to viscosity V 20 viscosity ratio (V) 2.0 / V 20 () as a thixotropic index.

[0200] (4) Volume resistivity

[0201] The obtained paste composition was coated onto a glass substrate (1 mm thick) with a thickness of 30 μm by screen printing. After drying at 120 °C for 10 minutes, the temperature was increased to 200 °C at a rate of 60 °C / min, and cured at 200 °C and 15 MPa for 2 minutes to obtain wiring.

[0202] The resistivity of the obtained wiring was measured using a resistivity meter (product name "MCP-T600", manufactured by Mitsubishi Chemical Corporation) via the four-terminal method.

[0203] (5) Shear strength

[0204] The obtained paste composition was stencil printed onto a copper frame and dried at 120°C for 10 minutes. A gold chip with a gold vapor-deposited coating on the back was then mounted onto a 2mm × 2mm bonding surface. The temperature was increased to 200°C at a rate of 60°C / min, and then cured under heat and pressure at 200°C and 15MPa for 2 minutes. The thermal shear strength at 260°C was measured using an installation strength measuring device.

[0205] (6) Hot and cold circulation

[0206] (Manufacturing of the joint)

[0207] The obtained paste composition was stencil printed onto a copper frame and dried at 120°C for 10 minutes. The gold silicon chip with a gold vapor deposition layer on the back was then mounted on the 5mm×5mm bonding surface. The temperature was increased to 200°C at a rate of 60°C / min, and then cured under heat and pressure at 200°C and 15MPa for 2 minutes to obtain the bonding body.

[0208] (Hot and cold cycle processing)

[0209] The resulting 10 joints were subjected to a thermal cycling treatment. As part of the thermal cycling treatment, a cycle was performed by holding at -55°C for 30 minutes, heating from -55°C to 150°C at a rate of 30°C / min, holding at 150°C for 30 minutes, and then cooling down at a rate of 30°C / min. This cycle was repeated 2000 times.

[0210] In the assembly that underwent the thermal cycling process, the presence or absence of silicon chip peeling was observed using an ultrasonic microscope (product name "FineSAT II", manufactured by Hitachi Power Solutions, Inc.), and evaluated according to the following criteria.

[0211] OK: Of the 10, 0 silicon chips were removed.

[0212] NG: Of the 10, more than one silicon chip was stripped off.

[0213] (7) Particle size distribution

[0214] For each ointment composition shown in Table 2, silver particles from the constituent components of the ointment composition were added in the proportions shown in Table 2 to obtain a sample for determining the particle size distribution of silver particles.

[0215] For example, the ointment composition of Example 2 was prepared by mixing 90 parts by weight of TC-728 and 10 parts by weight of TC-905 to obtain a test sample.

[0216] For each sample used in the test, the particle size distribution was measured using a laser diffraction particle size distribution measuring device (trade name "SALAD-7500nano", manufactured by Shimadzu Corporation). Based on this particle size distribution, the average particle size (D50) was calculated from the particle size of 50% of the cumulative volume (50% particle size D50).

[0217] Furthermore, based on this particle size distribution, the proportion of particles in three regions—below 1.0 μm, 1.0–20 μm, and above 20 μm—was calculated according to the frequency of the particle size distribution.

[0218] (8) Specific surface area

[0219] A sample for determining the specific surface area of ​​silver particles was prepared by performing the following operations: For each ointment composition shown in Table 2, only the silver particles in the composition of that ointment composition were added according to the proportions shown in Table 2 to obtain a sample for determining the specific surface area of ​​silver particles.

[0220] For example, the ointment composition of Example 2 was prepared by mixing 90 parts by weight of TC-728 and 10 parts by weight of TC-905 to obtain a test sample.

[0221] For each sample obtained for testing, after degassing at 60°C for 10 minutes, the specific surface area was determined by the BET single-point method based on nitrogen adsorption using a specific surface area measuring device (Monosorb, Quanta Chrome Instruments, USA).

[0222] (9) 5% weight reduction temperature

[0223] Each resin (jER-1009 and JP-100) was contained in a differential thermal and thermogravimetric analyzer (trade name "TG / DTA6200", manufactured by Hitachi Advanced Technology Co., Ltd.). The resin was heated from room temperature (25°C) at a heating rate of 10°C / min, and the temperature at which the weight of the resin decreased by 5% by mass was taken as the 5% weight reduction temperature of the resin.

[0224]

[0225] The variation rate of the microcrystalline particle size of the (111) surface of the paste composition of the embodiment ({((S1-S0) / S0)×100}) is more than 250%, and the content of silver particles with a particle size greater than 20 μm in 100% by mass of silver particles is less than 5% by mass. Therefore, it has good coatability, can be pressure bonded at low temperature, and has high adhesive strength.

[0226] On the other hand, the change rate of the paste compositions of Comparative Examples 1-3 and 5-8 {((S1-S0) / S0)×100} is less than 250%, therefore, at least one of the properties of spreadability, pressure bonding under low temperature conditions and adhesive strength is poor.

[0227] For the paste composition of Comparative Example 4, the content of silver particles with a particle size greater than 20 μm in 100% by mass of silver particles is greater than 5% by mass. Therefore, at least one of the following characteristics is poor: coatability, dispersibility, pressure bonding under low temperature conditions, and adhesive strength.

[0228] For the paste compositions of Comparative Examples 9-10, the content of silver particles (A) is less than 95% by mass in 100% of the total amount of silver particles (A) and adhesive (B). Therefore, at least one of the following characteristics is poor: coatability, dispersibility, pressure bonding under low temperature conditions, and adhesive strength.

Claims

1. A paste composition, wherein, The ointment composition comprises silver particles (A) and a binder (B). Of the 100% by mass of silver particles (A), the content of silver particles (Al) with a particle size greater than 20 μm is less than 5% by mass. Of the total amount of silver particles (A) and binder (B) in 100% by mass, the content of silver particles (A) is 95% by mass or more. The rate of change expressed by the following formula (1) is more than 250%. Rate of change = (S1 - S0) / S0 × 100 (%) (1) S0 is the crystallite size in Miller index (111) of the silver particles in the dried product of the ointment composition. S1 is the microcrystal size in Miller index (111) of silver particles in a treated product obtained by heating and pressurizing the dried product of the ointment composition at 15 MPa and 200 °C for 2 minutes under nitrogen environment.

2. The ointment composition according to claim 1, wherein, Of the 100% by mass of silver particles (A), the content of silver particles (A2) with a particle size of 1.0 to 20 μm is less than 50% by mass.

3. The ointment composition according to claim 1 or 2, wherein, Of the 100% by mass of silver particles (A), the content of silver particles (A3) with a particle size of less than 1.0 μm is more than 50% by mass.

4. The ointment composition according to any one of claims 1 to 3, wherein, The specific surface area of ​​the silver particles (A) is 1.4 m². 2 / g or more.

5. The ointment composition according to any one of claims 1 to 4, wherein, The adhesive (B) comprises one or more selected from thermosetting resins and thermoplastic resins.

6. The ointment composition according to any one of claims 1 to 5, wherein, The adhesive (B) has a 5% mass weight reduction temperature of 250°C or higher.

7. The ointment composition according to any one of claims 1 to 6, wherein, The ointment composition contains a solvent (C), Of the total amount of silver particles (A), adhesive (B), and solvent (C) in 100% by mass, the content of solvent (C) is 10-30% by mass.

8. A semiconductor device, wherein, The semiconductor device has a junction formed by the paste composition according to any one of claims 1 to 7.

9. A method for manufacturing a semiconductor device, wherein, It is a method for manufacturing a semiconductor device having semiconductor elements and semiconductor support components, the manufacturing method comprising: The process of applying the paste composition according to any one of claims 1 to 7 to the semiconductor support component; The process of mounting the semiconductor element onto the paste composition; as well as The process of heating and pressurizing the semiconductor element and the semiconductor support component to bond them together. The heating and pressurizing bonding conditions are carried out at 180–300°C and 1–30 MPa for 0.5–10 minutes.

10. An electronic component, wherein, The electronic component has a joint formed by the paste composition according to any one of claims 1 to 7.

11. A method for manufacturing an electronic component, wherein, The manufacturing method includes a step of forming a joint from the paste composition according to any one of claims 1 to 7.

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