CN109314320A

CN109314320A - Connection structural bodies, particle and bonding composition containing metallic atom

Info

Publication number: CN109314320A
Application number: CN201780038324.6A
Authority: CN
Inventors: 笹平昌男
Original assignee: Sekisui Chemical Co Ltd
Current assignee: Sekisui Chemical Co Ltd
Priority date: 2016-06-22
Filing date: 2017-06-22
Publication date: 2019-02-05
Anticipated expiration: 2037-06-22
Also published as: KR102446470B1; KR20190015527A; CN109314320B; TW201816802A; TWI783938B; WO2017222010A1; JPWO2017222010A1; JP2022184887A

Abstract

The present invention provides one kind and is able to suppress the generation of warpage and the connection structural bodies in crack and the particle and bonding composition containing metallic atom for assembling the connection structural bodies applying stress to it.The present invention provides a kind of connection structural bodies A, and with adhesive layer (50), the adhesive layer (50) is contained: the sintered body (10) of metallic and the particle (20) containing metallic atom.The particle (10) containing metallic atom and the sintered body (20) are contacted by chemical bond, in the section of the adhesive layer (50), 5% or more of the outer perimeter of the particle (10) containing metallic atom is contacted with the sintered body.

Description

Connection structural bodies, particle and bonding composition containing metallic atom

Technical field

The present invention relates to a kind of connection structural bodies, be used to form the connection structural bodies the particle containing metallic atom and Bonding composition.

Background technique

The nonisulated type semiconductor device of one of the known power semiconductor arrangement (power apparatus) for inverter etc. In, semiconductor element is fixed usually using connecting component.The connecting component can be one of electrode of semiconductor device.Example Such as, in the semiconductor device obtained by power transistor is installed in connecting component using Sn-Pb type welding mounting material, even The connecting component (base material) for connecing two connecting object components is the collector of power transistor.

In recent years, in the connection structural bodies of above-mentioned semiconductor device etc., it is expected that further improving its heat resisting temperature, heat passes The performances such as conductance, volume resistance.It is partly led by using the material other than above-mentioned welding mounting material to assemble for this purpose, also discussing The various methods of the connection structural bodies such as body device.As one of example, it is contemplated that use the material containing small particle metal Carry out the method (such as patent document 1 etc.) of assembly and connection structural body as connecting material.In the connecting material, clipped wire is utilized The following feature of son: the partial size of metallic becomes smaller to 100nm hereinafter, when composed atom number tails off, and surface area is with respect to particle The ratio of volume increases rapidly, and compared with integrality, fusing point or sintering temperature are greatly reduced.For example, surface is coated Organic matter and average grain diameter are that 100nm metallic below is used as connecting material, simultaneously by heat resolve organic matter Sintering metal particle and form adhesive layer, be thus connected two connecting object components.Metal in the connection method, after connection While particle variation is bulk metal, connection is realized by metallic bond on linkage interface, therefore can be further improved Heat resistance, connection reliability and the thermal diffusivity of connection structural bodies.

Existing technical literature

Patent document

Patent document 1: Japanese Unexamined Patent Publication 2013-55046 bulletin

Summary of the invention

Problem solved by the invention

However, in the connection structural bodies such as semiconductor device, due to the adhesive layer exposure of two connecting object components of connection In cold cycling condition, therefore when applying stress to the connecting object component of semiconductor wafer and semiconductor chip etc., it is easy Generate warpage and crack.For example, in collector, it is brilliant due to passing through several amperes or more of electric current during semiconductor device work Body tube chip generates heat and generates thermal stress, therefore there are problems that warpage occurs for semiconductor chip.In addition to patent document 1 etc., also Several connecting materials for assembly and connection structural body are proposed, but are not gone out from the viewpoint for preventing stress from leading to warpage and crack Hair attempts improvement connecting material.Therefore, it is desirable to construct at this stage and is able to suppress warpage applying stress to it It generates and crack and the more excellent high-performance connection structural bodies of durability.

The present invention is to complete in view of the above problems, and its purpose is to provide one kind can applying stress to it Inhibit the generation of warpage and the connection structural bodies in crack and the particle containing metallic atom for assembling the connection structural bodies And bonding composition.

Technical means to solve problem

The present inventor has made intensive studies to achieve the above object, as a result, it has been found that, connection structural bodies in order to prevent Warpage and crack, the stress that mitigation is applied to the adhesive layer of two connection structural bodies of connection in connection structural bodies are critically important.Also, Further investigation the result shows that, by making adhesive layer contain the particle with stress abirritation, at the same make the particle surface and The contact area for constituting the sintered body of adhesive layer is bigger than previous, it is possible thereby to reach above-mentioned purpose thereby completing the present invention.

That is, the present invention is including, for example, theme documented by following item.

1, a kind of bonded structure, with adhesive layer, above-mentioned adhesive layer contains: the sintered body of metallic and containing Metallic atom particle, wherein

Above-mentioned particle containing metallic atom and above-mentioned sintered body are contacted by chemical bond,

In the section of above-mentioned adhesive layer, the outer perimeter of the above-mentioned particle containing metallic atom 5% or more with above-mentioned sintered body Contact.

2, according to the above-mentioned bonded structure of item 1, wherein above-mentioned particle containing metallic atom is with substrate particle and configuration Metal portion on above-mentioned substrate particle surface.

3, according to the above-mentioned bonded structure of item 2, wherein above-mentioned metal portion has multiple protrusions in outer surface.

4, according to the above-mentioned bonded structure of item 3, wherein the average diameter of the base portion of above-mentioned protrusion be 3nm or more and 5000nm or less.

5, according to the above-mentioned bonded structure of item 3 or 4, wherein the average height of above-mentioned protrusion be 1nm or more and 1000nm or less.

6, according to the above-mentioned bonded structure of any one of item 3~5, wherein the summary table of the outer surface of above-mentioned metal portion In area 100%, above-mentioned protrusion accounts for 30% or more.

7, according to the above-mentioned bonded structure of any one of item 2~6, wherein in above-mentioned metal portion, nickel, chromium, platinum and rhodium Total amount relative to above-mentioned metal portion gross mass be 30 mass % or less.

8, according to the above-mentioned bonded structure of any one of item 2~7, wherein above-mentioned metal portion contain selected from gold, silver, One or more of tin, copper, germanium, indium, palladium, tellurium, thallium, bismuth, zinc, arsenic, selenium and alloy containing these metallic elements.

9, according to the above-mentioned bonded structure of any one of item 2~8, wherein formed on the surface of above-mentioned substrate particle There are multiple recess portions.

Item 10, a kind of particle containing metallic atom, are used for the above-mentioned bonded structure of any one of item 1~9.

Item 11, a kind of bonding composition, contain item 10 above-mentioned particle containing metallic atom and metallic.

Invention effect

In connection structural bodies of the invention, even if applying stress to connection structural bodies, it is also difficult to warpage and crack occurs, because This excellent in te pins of durability.Therefore, connection structural bodies through the invention, such as the power of high reliablity and function admirable can be provided Device.

Particle containing metallic atom of the invention is suitable as assembling the material of above-mentioned connection structural bodies, provides and be difficult to Generate the connection structural bodies of warpage and crack.

Detailed description of the invention

Fig. 1 shows an examples of the connection structural bodies of present embodiment, are the schematic diagrames in the section of connection structural bodies.

Fig. 2 indicates an example of the structure of the particle containing metallic atom, is the signal of its appearance and partial cross section Figure.

Fig. 3 indicates other examples of the structure of the particle containing metallic atom, is the signal of its appearance and partial cross section Figure.

Fig. 4 indicates other examples of the structure of the particle containing metallic atom, is the signal of its appearance and partial cross section Figure.

Fig. 5 indicates other examples of the structure of the particle containing metallic atom, is the signal of its appearance and partial cross section Figure.

Fig. 6 (a) is the schematic diagram of the cross section structure of the adhesive layer of the connection structural bodies of present embodiment, and Fig. 6 (b) is existing The schematic diagram of the cross section structure of the adhesive layer of connection structural bodies.

Specific embodiment

Hereinafter, embodiments of the present invention be will be explained in.It should be noted that in the present specification, about " containing Have " and "comprising" expression, comprising " containing ", "comprising", " substantially by ... constituted " and " only by ... constituted " it is general It reads.

Fig. 1 shows an examples of the connection structural bodies of present embodiment, schematically show the section of connection structural bodies.

The connection structural bodies of present embodiment has adhesive layer, and above-mentioned adhesive layer includes the sintered body of metallic and contains There is the particle of metallic atom, wherein the above-mentioned particle containing metallic atom and above-mentioned sintered body are contacted by chemical bond, above-mentioned In the section of adhesive layer, 5% or more of the outer perimeter of the above-mentioned particle containing metallic atom is contacted with above-mentioned sintered body.

For the connection structural bodies of present embodiment, the sintered body of particle and metallic containing metallic atom is connect Contacting surface product is very big, and therefore, even if applying stress to connection structural bodies, connection structural bodies is also difficult to happen warpage and crack.Therefore, Connection structural bodies has excellent durability.

Connection structural bodies A shown in FIG. 1 includes the first connecting object component 51, the second connecting object component 52 and connection The adhesive layer 50 of first connecting object component and the second connecting object component.First connecting object component 51 and the second connecting object Component 52 realizes connection by adhesive layer 50.

Adhesive layer 50 includes the sintered body 20 of particle 10 and metallic containing metallic atom and is formed.In addition, such as this The connection structural bodies A of embodiment, adhesive layer 50 can control particle 30 containing gap.Gap controls the partial size of particle 30 and glues The thickness for connecing layer 50 is identical, in other words, may be used as the first connecting object component 51 and the second connecting object component 52 it Between spacer.Gap controls particle 30, can be used, for example, as well known conducting particles, but not limited to this.

As above-mentioned connecting object component 51 and 52, specifically, can enumerate: semiconductor chip, capacitor and diode The ministry of electronics industry of the equal circuit boards such as electronic components and printed base plate, flexible printed board, glass epoxy substrate and glass substrate etc. Part etc., but it is not limited to above content.Above-mentioned connecting object component 51,52 is preferably electronic component.

In addition, at least one of the first connecting object component 51 and the second connecting object component 52 are preferably semiconductor die Piece or semiconductor chip.That is, connection structural bodies A is preferably semiconductor device.

The sintering of the particle 10 and metallic containing metallic atom contained by adhesive layer 50 is described in detail below The composition of body 20.It should be noted that in the following description, omitting the appended drawing reference in Fig. 1 sometimes.

Particle containing metallic atom can form chemical bond with the sintered body of metallic, and type has no especially Limitation.

For example, the gold that the particle containing metallic atom is preferably provided with substrate particle and is configured on above-mentioned substrate particle surface Category portion.In this case, the particle containing metallic atom is easy to form chemical bond, especially metal with the sintered body of metallic Key, more specifically, the metal portion of the particle surface containing metallic atom and the sintered body of metallic can form so-called Solid solution, the particle containing metallic atom and sintered body more firmly realize connection as a result, to be easier to inhibit connection structure The generation of the warpage of body and crack.

The type of above-mentioned substrate particle is not particularly limited.Such as it can enumerate: resin particle, the nothing in addition to metallic Machine particle, organic-inorganic stuff and other stuff and metallic etc..Above-mentioned substrate particle be preferably resin particle, except metallic with Outer inorganic particulate or organic-inorganic stuff and other stuff.

It is suitable for using various organic as the material for forming resin particle in the case where substrate particle is resin particle Object.As the material, such as can enumerate: polyethylene, polystyrene, polyorganosiloxane resin, polyvinyl chloride, gathers inclined two at polypropylene The polyolefin resins such as vinyl chloride, polyisobutene, polybutadiene；The acrylic acid tree such as polymethyl methacrylate, polymethyl acrylate Rouge；Polyalkylene terephthalates, polysulfones, polycarbonate, polyamide, phenolic resin, melamine resin, benzocarbamidine Amine-formaldehyde resins, urea formaldehyde resin, phenolic resin, melamine resin, benzoguanamine resin, epoxy resin, saturated polyester tree Rouge, unsaturated polyester resin, polyphenylene oxide, polyacetals, polyimides, polyamidoimide, polyether-ether-ketone, polyether sulfone, urea tree Rouge etc..

In addition, resin particle can pass through the one or more kinds of various polymerisms with ethylenically unsaturated group of polymerization Monomer and obtain.In such a case it is possible to which design and synthesis have the resin particle of following physical property, that is, arbitrarily compressed When be suitable for anisotropic conductive material physical property.In addition, in such a case it is possible to easily by substrate particle Hardness controls in preferred scope.From this viewpoint, the material of above-mentioned resin particle is one or two kinds of preferably by polymerization Polymer obtained from polymerizable monomer with multiple ethylenically unsaturated groups above.

When by polymerize have ethylenically unsaturated group monomer to obtain above-mentioned resin particle when, as with olefinic not The monomer of saturated group can enumerate the monomer of non-crosslinked property and/or the monomer of bridging property.It should be noted that in following explanation In, " (methyl) acrylic acid " refers to one or both of " acrylic acid " and " methacrylic acid ", and " (methyl) acrylate " refers to " third One or both of olefin(e) acid ester " and " methacrylate ".

As above-mentioned non-crosslinked property monomer, following substance can be enumerated.Such as vinyl compound, it can enumerate: benzene second The styrene monomers such as alkene, α-methylstyrene, chlorostyrene；Methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl The vinyl ethers such as ether, 1,4- butanediol divinyl ether, cyclohexanedimethanol divinyl base ether, diethylene glycol divinyl ether Class；The vinyl acetates class such as vinyl acetate, vinyl butyrate, vinyl laurate, stearic acid vinyl ester；Vinyl chloride and vinyl fluoride Deng the monomer containing halogen；It as (methyl) acyclic compound, can enumerate: (methyl) methyl acrylate, (methyl) acrylic acid Ethyl ester, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) 2-EHA, (methyl) acrylic acid moon Osmanthus ester, (methyl) aliphatic acrylate, (methyl) stearyl acrylate, (methyl) cyclohexyl acrylate, (methyl) propylene Sour isobornyl thiocyanoacetate etc. (methyl) alkyl-acrylates；(methyl) acrylic acid 2- hydroxyl ethyl ester, (methyl) glycerol acrylate, (first Base) (methyl) esters of acrylic acid containing oxygen atom such as acrylic ester, (methyl) glycidyl acrylate；(first Base) monomer containing nitrile such as acrylonitrile；(methyl) acrylic acid trifluoromethyl ester, five fluorine ethyl ester of (methyl) acrylic acid etc. contain halogen (methyl) esters of acrylic acid；It as alpha-olefin compound, can enumerate: diisobutylene, isobutene, linear alpha-olefin, ethylene, propylene etc. Olefines；As conjugated diene compound, isoprene, butadiene etc. can be enumerated.

As above-mentioned cross-linkable monomer, following substance can be enumerated.Such as it as vinyl compound, can enumerate: divinyl The vinyl monomers such as base benzene, 1,4- divinyl oxygroup butane, divinylsulfone；As (methyl) acyclic compound, can lift Out: tetramethylol methane four (methyl) acrylate, tetramethylol methane three (methyl) acrylate, tetramethylol methane two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, dipentaerythritol six (methyl) acrylate, two seasons penta Tetrol five (methyl) acrylate, three (methyl) glycerol acrylates, two (methyl) glycerol acrylates, (poly-) ethylene glycol two (methyl) acrylate, (poly-) propylene glycol two (methyl) acrylate, (poly-) tetramethylene glycol two (methyl) acrylate, 1, The multifunctional (methyl) acrylates classes such as 4- butanediol two (methyl) acrylate；As allyl compound, can enumerate: triolefin Propyl (different) cyanurate, triallyltrimelitate, diallyl phthalate, diallyl acrylamide, two allyls Base ether；It as polysiloxane compound, can enumerate: tetramethoxy-silicane, tetraethoxysilane, triethylsilane, tert-butyl two Methyl-monosilane, methyltrimethoxysilane, methyltriethoxysilane, ethyl trimethoxy silane, ethyl triethoxysilane, Isopropyltri-methoxysilane, trimethoxysilane, cyclohexyl trimethoxy silane, n-hexyl trimethoxy silane, N-octytriethoxysilane, positive decyl trimethoxy silane, phenyltrimethoxysila,e, dimethyldimethoxysil,ne, two Methyldiethoxysilane, diisopropyl dimethoxy silane, trimethoxysilyl styrene, γ-(methyl) acryloyl Oxygroup propyl trimethoxy silicane, 1,3- divinyl tetramethyl disiloxane, aminomethyl phenyl dimethoxysilane, diphenyl two The silanols salt such as methoxy silane；Vinyltrimethoxysilane, vinyltriethoxysilane, dimethoxy-methyl ethylene Base silane, dimethoxy-ethyl vinyl silanes, diethoxymethyl divinyl silane, diethoxy ethyl vinyl silicon Alkane, ethyl-methyl divinyl silane, methylvinyldimethoxysilane, ethyl vinyl dimethoxysilane, methyl second Alkenyl diethoxy silane, ethyl vinyl diethoxy silane, to styryltrimethoxysilane, 3- methacryloxypropyl Base hydroxypropyl methyl dimethoxysilane, 3- methacryloxypropyl trimethoxy silane, 3- methacryloxypropyl Methyldiethoxysilane, 3- methacryloxypropyl, 3- acryloxypropyl trimethoxy silicon The silane alkoxide containing polymeric double bond such as alkane；The annular siloxanes such as decamethylcyclopentaandoxane；Single terminal-modified silicone oil, two ends Hold modified (reactivity) silicone oil such as silicone oil and side chain type silicone oil；The carboxylic lists such as (methyl) acrylic acid, maleic acid, maleic anhydride Body etc..

Bridging property and non-crosslinked property monomer are not limited to the monomer enumerated above, are also possible to other polymerizable monomers, example Such as, it is also possible to well known polymerizable monomer.

It polymerize the above-mentioned polymerizable monomer with ethylenically unsaturated group by known method, to obtain above-mentioned resin particle Son.As this method, for example, suspension polymerisation in the presence of radical polymerization initiator method, use noncrosslinking kind of particle Method (so-called seeded polymerization) polymerizeing be swollen monomer together with radical polymerization initiator etc..These polymerization sides The condition of method is not particularly limited, can be with generally applicable well known condition.

In the case where above-mentioned substrate particle is inorganic particulate or organic-inorganic stuff and other stuff in addition to metallic, make For material, that is, inorganic material of substrate particle, silica and carbon black etc. can be enumerated.The inorganic material is not preferably metal.By upper The particle for stating silica formation is not particularly limited, such as can enumerate, and has more than two water-disintegrable alkoxy first in hydrolysis After the silicon compound of silylation is to form cross-linking polymer particle, particle obtained from being fired as needed.As above-mentioned Organic-inorganic stuff and other stuff, such as can enumerate, had by what the alkoxysilyl polymer and acrylic resin that are crosslinked were formed Inorganic stuff and other stuff of machine etc..

The other examples of the material of particle as above-mentioned base material can enumerate the resin containing polyrotaxane.Polyrotaxane refers to, chain The structure that macromolecule is formed through the opening portion of ring molecule.The type of polyrotaxane is not particularly limited, such as can enumerate public affairs The polyrotaxane known.

When the material for constituting substrate particle is the resin containing polyrotaxane, polyrotaxane is preferably cross-linking agent.Specifically, It is preferred that ring molecule in polyrotaxane and the ring molecule in other polyrotaxanes be crosslinked by macromolecular chain made of structure.As long as It is above-mentioned crosslinked polyrotaxane, the flexibility of substrate particle can improve, therefore be easy to play stress alleviation effects, to be easy to press down The crack of connection structural bodies processed and the generation of warpage.Therefore, even as the polyrotaxane of such cross-linking agent, type does not have yet There is special limitation, for example, well known crosslinked polyrotaxane can be enumerated.

Above-mentioned polyrotaxane, such as can be made by well known method.For example, by making containing with polymerizable functional group The polyrotaxane of ring molecule reacted with the mixture that polymerizable monomer is formed, to prepare the poly- wheel with cross-linked structure Alkane.The reaction, such as can be carried out by well known method.

The type of polyrotaxane containing the ring molecule with polymerizable functional group is not particularly limited.As specific reality Example, can enumerate: " SeRM (registered trademark) SuperpolymerSM3405P " of AdvancedSoftMaterials companies market, " SeRM (registered trademark) KeyMixtureSM3400C ", " SeRM (registered trademark) SuperpolymerSA3405P ", " SeRM (registered trademark) SuperpolymerSA2405P ", " SeRM (registered trademark) MixtureSA3400C ", " SeRM (registered trademark) KeyMixtureSA2400C ", " SeRM (registered trademark) SuperpolymerSA3405P ", " SeRM (registered trademark) Superpolymer SA2405P " etc..

The average grain diameter of substrate particle is not particularly limited, such as the thickness of adhibited layer that it can be made to be less than connection structural bodies 1/2.In the average grain diameter of substrate particle in the case where above range, it is difficult to warpage and the crack of adhesive layer occurs, it is also difficult The reduction of the bonding force of adhesive layer occurs.

In addition, the average grain diameter of substrate particle is preferably also 0.1 μm or more and 55 μm or less.In this case, cold and hot Connection structural bodies is difficult to happen crack and warpage in circulation, and the bonding force of adhesive layer is then also difficult to happen in thermal cycling test Reduction.The average grain diameter of substrate particle is preferably 0.5 μm or more, more preferably 1 μm or more, and preferably 40 μm hereinafter, More preferably 10 μm hereinafter, particularly preferably 6 μm or less.

It should be noted that the average grain diameter of substrate particle can be identical as the thickness of adhesive layer.In this case, contain The particle of metallic atom can also play the role of control particle 30 in gap illustrated in fig. 1.

The average grain diameter of above-mentioned substrate particle refers to diameter when shape is ball, is in the shape in addition to spheroidal Refer to the average value of maximum diameter and minimum diameter.In addition, the average grain diameter of substrate particle refers to, seen by scanning electron microscope Substrate particle is examined, measures the partial size of randomly selected 50 substrate particles with vernier caliper and the average value that acquires.It needs to illustrate , when coating substrate particle as described above with other materials (for example, metal portion), average grain diameter also includes its clad.

The coefficient of variation (CV value) of the partial size of substrate particle is, for example, 50% or less.Under the above-mentioned coefficient of variation (CV value) passes through Formula indicates.

CV value (%)=(ρ/Dn) × 100

ρ: the standard deviation of particle diameter

Dn: the average value of particle diameter

For further suppressing the viewpoint in the crack of connection structural bodies or the generation of removing, the CV of the partial size of substrate particle Value preferably 40% is hereinafter, more preferably 30% or less.The lower limit of the CV value of the partial size of substrate particle is not particularly limited.It is above-mentioned CV value can be 0% or more, be also possible to 5% or more, be also possible to 7% or more, be also possible to 10% or more.

The hardness of substrate particle is not particularly limited, such as 10%K value is 10N/mm²Above and 3000N/mm²Below.Just For the viewpoint for further suppressing the crack of connection structural bodies and the generation of warpage, 10%K value is preferably 100N/mm²More than, more Preferably 1000N/mm²More than, and preferably 2500N/mm²Hereinafter, particularly preferably 2000N/mm²Below.

10%K value herein is modulus of elasticity in comperssion when substrate particle is compressed 10%.It can be in the following manner Measurement.Firstly, using micro- compressing tester, on the smooth pressure head end face of cylindrical body (50 μm of diameter, diamond fabrication), 25 Apply under the loading condiction that 60 seconds maximum test loads are 20mN at DEG C, compresses substrate particle.Measurement load value (N) at this time and Compression displacement (mm).It, can be in the hope of above-mentioned modulus of elasticity in comperssion by following equation according to obtained measured value.

10%K value (N/mm²)=(3/2^1/2)·F·S^-3/2·R^-1/2

F: the load value (N) when particle is by compressive deformation 10%

S: the compression displacement (mm) when particle is by compressive deformation 10%

R: particle radii (mm)

As above-mentioned micro- compressing tester, such as " FischerScopeH-100 " etc. that is manufactured using Fischer company. It should be noted that can be carried out by above-mentioned each parameter when finding out particle compressive deformation 30% when calculating 30%K value It calculates.

Substrate particle is preferably, and in every 1,000,000 particles, aggregated particle is 100 or less.The particle of above-mentioned cohesion is 1 The particle that a particle connects at least one other particles.Such as there are 3 grains comprising 3 cohesions in every 1,000,000 substrate particles In the case where the particle (condensate of 3 particles) of son, in every 1,000,000 substrate particles, the quantity of the particle of cohesion is 9. It as the measuring method of above-mentioned aggregated particle, can enumerate, using being set with the particle that about 50,000 can be observed under 1 visual field Multiplying power microscope, aggregated particle is counted, in total method etc. to measure aggregated particle under 20 visuals field.

Substrate particle preferably has 200 DEG C or more of thermal decomposition temperature.In this case, connection knot is formed as described below When the adhesive layer of structure body, it is easy to inhibit the thermal decomposition of substrate particle.The thermal decomposition temperature of substrate particle is preferably 220 DEG C or more, More preferably 250 DEG C or more, further preferably 300 DEG C or more.It should be noted that there is aftermentioned cladding in substrate particle In the case where layer, using the temperature first thermally decomposed in substrate particle and clad as the thermal decomposition temperature of substrate particle.

On the surface of substrate particle, metal portion can be configured.Such as metal portion is to coat the side on the surface of substrate particle Formula exists.

Metal portion is formed by wrapping metalliferous material.As the metal, for example, can enumerate gold, silver, tin, copper, germanium, indium, palladium, Tellurium, thallium, bismuth, zinc, arsenic, selenium, iron, lead, ruthenium, aluminium, cobalt, titanium, antimony, cadmium, silicon, nickel, chromium, platinum, rhodium etc..Metal portion can be only these One of metal, can also be containing more than two of them.In addition, metal portion can be it is two or more in above-mentioned each metal The alloy of metal.Contained metal phase for metal portion gross mass be 50 mass % or more, preferably 80 mass % or more, it is more excellent It is selected as 90 mass % or more, particularly preferably 99 mass % or more.In addition, metal portion can be formed only by metal.

In metal portion, nickel, chromium, platinum and rhodium total amount relative to the gross mass of above-mentioned metal portion be preferably 30 mass % with Under.

Above-mentioned nickel, chromium, platinum and rhodium total amount relative to above-mentioned metal portion gross mass within the above range when, sintered body, Especially in the case where constituting the particle of sintered body is silver, it is easy to spread metal, as a result, the particle containing metallic atom More easily contacted with sintered body.

Gross mass of the total amount relative to above-mentioned metal portion of nickel, chromium, platinum and rhodium, preferably 25 mass % are hereinafter, more preferably For 20 mass % hereinafter, further preferably 10 mass % are hereinafter, particularly preferably 0 mass %.In above-mentioned metal portion, nickel, chromium, The total amount of platinum and rhodium relative to above-mentioned metal portion gross mass in above-mentioned each range when, the particle containing metallic atom especially holds Easily contacted with sintered body.

Metal portion preferably comprises at least one selected from following compositions: gold, silver, tin, copper, germanium, indium, palladium, tellurium, thallium, bismuth, Zinc, arsenic, selenium and the alloy containing one or more of these metallic elements.In this case, containing the particle of metallic atom It is easier to contact with the sintered body of metallic, and the generation of warpage and crack in connection structural bodies can be further suppressed.

Particularly preferred metal portion contains the metal that pyroconductivity is 200W/mK or more.In the case where containing the metal, More easily inhibit the generation of warpage and crack in connection structural bodies, and thermal diffusivity can also be improved.As the metal, such as can It enumerates selected from one of gold, silver and copper.

Metal portion can be formed by one layer, can also be formed by multilayer.

Metal portion is preferably the so-called multilayered structure formed by multilayer.The metal for including in each layer can be different.Such as gold Category portion can be formed as double-layer structure.

Fig. 2 schematically shows the appearance of the particle containing metallic atom, which, which has, is formed as The metal portion of double-layer structure.It should be noted that the partial cross section structure in order to indicate the particle containing metallic atom, in Fig. 2 In, the fragmentary perspective that dotted line part is surrounded indicates.

The particle 10 containing metallic atom of form shown in Fig. 2 includes substrate particle 11 and metal portion 12.Metal portion 12 with The mode for coating the surface of substrate particle 11 is configured.In addition, metal portion 12 is formed to have the first metal portion 12a and second The double-layer structure of metal portion 12b, by the first metal portion 12a inside, the second metal portion 12b on the outside in a manner of configured. That is, being contacted with the first metal portion 12a with the surface of substrate particle 11, the second metal portion 12b coats the first surface metal portion 12a Mode exists.

Particle 10 containing metallic atom, when there is the metal portion of double-layer structure as shown in the form of Fig. 2, the first metal portion 12a and the second metal portion 12b particularly preferably contain selected from one or more of gold, silver and copper.As specific example, the first metal Portion 12a contains copper, and the second metal portion 12b contains silver.Since the second metal portion 12b is silver, with the sintered body of metal Contact area is easier to become larger, it is easier to contact with the sintered body of metal.In addition, in the case where the first metal portion 12a is copper, The usage amount of the silver of the second metal portion 12b can be reduced, thus more advantageous for economic angle.

In particle containing metallic atom used in the connection structural bodies of present embodiment, the thickness of above-mentioned metal portion is excellent Be selected as 0.5nm or more, more preferably 10nm or more, and preferably 10 μm hereinafter, more preferably 1 μm hereinafter, further preferably For 500nm hereinafter, particularly preferably 300nm or less.When the thickness of metal portion is more than above-mentioned lower limit and below the above-mentioned upper limit, Particle containing metallic atom is easier to spread more evenly across in the sintered body of metallic, and is easier to connect with sintered body Touching (that is, the particle containing metallic atom increases relative to the contact area of sintered body), therefore connection knot can be further suppressed The generation of the warpage of structure body and crack.It is each layer in the case where metal portion is multilayer for the thickness of above-mentioned metal portion Overall thickness, i.e. the thickness of metal portion entirety.

In particle containing metallic atom used in the connection structural bodies of present embodiment, in the table of above-mentioned substrate particle There is no particular restriction for the method for formation metal portion on face.As the method for forming metal portion, such as it can enumerate and pass through electroless plating Method, the method by plating, the method by physical vapour deposition (PVD) and by metal powder or contain metal powder and viscous The paste coating of mixture is in the method etc. on the surface of substrate particle.For the viewpoint of the simplicity of the formation of metal portion, preferably Pass through the method for electroless plating.As the method above by physical vapour deposition (PVD), can enumerate vacuum vapor deposition, ion plating, The methods of ion sputtering.

In metal portion situation with multi-layer structure, metal portion can be formed by identical method.Such as by adopting With the forming method of above-mentioned metal portion, the metal portion of first layer is formed on substrate particle surface, on the surface of first layer according to It is secondary to form next layer, metal portion with multi-layer structure can be formed.

It should be noted that the form of above-mentioned metal portion is only an example, in addition, the particle containing metallic atom can have There is the metal portion other than above-mentioned form.

Above-mentioned metal portion can have multiple protrusions in outer surface.

Fig. 3 schematically shows the appearance for having the particle containing metallic atom of metal portion, and above-mentioned metal portion is in outer surface With multiple protrusions.It should be noted that the partial cross section structure in order to indicate the particle containing metallic atom will in Fig. 3 The fragmentary perspective that dotted line part surrounds indicates.

Particle 10 shown in the form of Fig. 3 containing metallic atom includes substrate particle 11 and metal portion 12.Metal portion 12 It is configured in a manner of coating the surface of substrate particle 11.In addition, metal portion 12 is formed to have the first metal portion 12a and The double-layer structure of two metal portion 12b, by the first metal portion 12a inside, the second metal portion 12b on the outside in a manner of matched It sets.That is, being contacted with the first metal portion 12a with the surface of substrate particle 11, the second metal portion 12b coats the first metal portion 12a table The mode in face exists.Can make the metal portion for being formed as double-layer structure 12 composition and above-mentioned Fig. 2 shown in form contain metal The composition having the same of atomic particle 10.

Multiple protrusions 13 are formed on the outer surface of metal portion 12.Protrusion 13 is using base portion as bottom surface, from the base portion to table Surface side mode outstanding and formed.Since there are multiple protrusions 13, the burning of particle and metallic containing metallic atom Knot body is easier to contact, as a result, being easy to inhibit the generation of the warpage of connection structural bodies and the generation in crack.It needs to illustrate It is that form the position of above-mentioned base portion be on the surface of metal portion 12.

As the forming method of above-mentioned protrusion, there is no particular restriction.Such as well known method can be used.Specifically, It can enumerate: after so that core material is attached to the surface of substrate particle, pass through the method for electroless plating formation metal portion；And in substrate grain After the surface of son forms metal portion by electroless plating, adhere to core material, then forms the method etc. of metal portion by electroless plating. In addition, can be enumerated as the other methods for forming above-mentioned protrusion:, will after forming the first metal portion on the surface of substrate particle Core material is configured in first metal portion, the method for then forming the second metal portion, and is formed on the surface of substrate particle The method etc. of the intermediate stage addition core material of metal portion.

It as the method for making core material be attached to above-mentioned substrate particle surface, can enumerate: be added to the dispersion liquid of substrate particle Core material, such as the method for making core material assemble and be attached to substrate particle surface by Van der Waals force；And there is substrate grain to addition Core material is added in the container of son, the surface for making core material be attached to substrate particle due to rotating etc. the mechanism of generations because of container Method etc..Wherein, it is easy for for the viewpoint of the amount of the core material of control attachment, preferably assembles core material and be attached to dispersion liquid In substrate particle surface method.If in core material insertion metal portion, it can the easily shape on the outer surface of metal portion At protrusion.

As the material of above-mentioned core material, conductive material and non-conductive material can be enumerated.As above-mentioned conductive material, It can enumerate: the electrically conductive, non-metallics such as metal, metal oxide, graphite and electric conductive polymer etc..As above-mentioned conductive poly Object is closed, polyacetylene etc. can be enumerated.As above-mentioned non-conductive material, silica, aluminium oxide, zirconium oxide etc. can be enumerated.Wherein, It is easy for for the viewpoint contacted with sintered body, preferably metal.Above-mentioned core material is preferably metallic.As under above situation Metal, the above-mentioned various metals that can constitute metal portion can be enumerated.More preferably with constitute metal portion outermost metal kind Class is identical.Therefore, the metal of protrusion is constituted, particularly preferably containing selected from one or more of gold, silver and copper.

There is no particular restriction for the shape of above-mentioned core material.Core material is preferably shaped to bulk.As core material, can enumerate: particle Cohesion block and unsetting block etc. made of the block of shape, the cohesion of multiple fine particles.

The average diameter (average grain diameter) of above-mentioned core material is preferably 0.001 μm or more, and more preferably 0.05 μm or more, and Preferably 0.9 μm hereinafter, more preferably 0.2 μm or less.The average diameter (average grain diameter) of above-mentioned core material indicates number average diameter (number Equal partial size).The average diameter of core material, by being averaged with electron microscope or optical microphotograph sem observation 50 any core materials and calculating It is worth and acquires.When measuring the average diameter of the core material in the particle containing metallic atom, such as can survey in the following manner Determine the average diameter of core material.Particle containing metallic atom is added in " Technovit4000 " of Kulzer company manufacture And make its dispersion, and make the 30 weight % of content of the particle containing metallic atom, metallic atom is contained for detecting with preparation Particle embedded resin.It is cut out using ion milling machine (" IM4000 " of Hitachi High-Technologies Corporation manufacture) containing metal The section of atomic particle, and the center for cutting through the particle containing metallic atom dispersed in the detection embedded resin is attached Closely.Then, using electric field emission type scanning electron microscope (FE-SEM), 50,000 times are configured by image multiplying power, random selection 20 A particle containing metallic atom observes 20 protrusions of the respectively particle containing metallic atom respectively.It measures resulting containing gold Belong to the diameter of the core material in atomic particle, and carries out arithmetic average using the average diameter as core material.

There is no particular restriction for the shape of protrusion, such as can be spherical or ellipse protrusion with Formation cross-section, can also be with shape At closer to the sharper nadel in front end.The shape of the protrusion, such as can be controlled according to the material of core material etc..

The average height of protrusion can be 1nm or more and 1000nm hereinafter, preferably 5nm or more, more preferably 50nm with On, and preferably 900nm is hereinafter, more preferably 500nm or less.When above-mentioned protrusion average height more than above-mentioned lower limit and When below the above-mentioned upper limit, the particle containing metallic atom is easier to contact with sintered body.

The average height of protrusion, such as can be measured in the following way.By the particle addition containing metallic atom In " Technovit4000 " manufactured to Kulzer company and make its dispersion, and makes the content of the particle containing metallic atom For 30 weight %, it is used to detect the embedded resin of the particle containing metallic atom with preparation.Use ion milling machine (the high-new skill of Hitachi " IM4000 " of art Co., Ltd. manufacture) section of the particle containing metallic atom is cut out, and cut through the detection embedded resin The immediate vicinity of the particle containing metallic atom of middle dispersion.Then, using electric field emission type scanning electron microscope (FE- SEM), 50,000 times are configured by image multiplying power, randomly chooses 20 particles containing metallic atom, observes respectively contain metal respectively 50 protrusions of atomic particle.Height using the base portion of protrusion bottom surface to projecting tip and is carried out as the height of protrusion Arithmetic average is using the average height as above-mentioned protrusion.

The average diameter of the base portion of protrusion can be 3nm or more and 5000nm hereinafter, preferably 50nm or more, more preferably 80nm or more, and preferably 1000nm is hereinafter, more preferably 500nm or less.The average diameter of base portion is herein, with it is above-mentioned The value that the identical sequence of the measuring method of the average height of protrusion acquires, that is, distinguished by using the FE-SEM of embedded resin The protrusion for observing randomly selected 20 particles containing metallic atom, measures the distance between each base portion both ends, and calculated It is worth obtained from art is average.

In the total surface area 100% of the outer surface of metal portion, above-mentioned protrusion can account for 30% or more.At this point, containing metal Atomic particle, it is easier to be contacted with sintered body.Occupied area of the protrusion relative to metal portion outer surface, such as can be by such as Under type measurement.Firstly, with the positive throwing of particle of field emission type scanning electron microscope (FE-SEM) shooting containing metallic atom Shadow figure.With 6000 times of photo of commercially available image analysis software analysis FE-SEM shooting.At the image planarize etc. Then reason, obtains the area (area in plan view) of protrusion, and by the area of protrusion and contain metallic atom Particle area occupied area of the ratio as protrusion.Find out in 20 particles containing metallic atom, protrusion relative to The occupied area of the outer surface of metal portion.

As other forms of the particle containing metallic atom, can have the substrate particle with recess portion and be configured at base Metal portion on material particle surface.In the particle containing metallic atom of the form, metal portion can also be formed in recess portion.With Under, specific example will be enumerated and be illustrated.

Fig. 4 indicates an example of the particle 10 containing metallic atom, and schematically shows the grain containing metallic atom The appearance of son 10 is somebody's turn to do the particle 10 containing metallic atom and has the substrate particle 11 with recess portion 14 and be configured at substrate particle 11 Surface on metal portion 12.It should be noted that scheming for the partial cross section structure for indicating the particle 10 containing metallic atom In 4, the fragmentary perspective for surrounding dotted line part is indicated.

In the particle 10 containing metallic atom shown in the form of Fig. 4, multiple recess portions 14 are formed in the table of substrate particle 11 On face.Metal portion 12 is configured in a manner of coating the surface of substrate particle 11.In the form, metal portion 12 is with the first metal portion 12a is configured in inside, the mode of the second metal portion 12b on the outside.That is, with the first metal portion 12a and substrate particle 11 The mode on the surface that surface contact, the second metal portion 12b coat the first metal portion 12a exists.Be formed as the metal of double-layer structure The composition in portion 12, can be identical as the composition of particle 10 containing metallic atom of form shown in above-mentioned Fig. 2.

Metal portion 12 can also be formed in the surface of recess portion 14.In the form of Fig. 4, the first metal portion 12a is formed in recessed Portion 14.

It is formed on the surface of the above-mentioned substrate particle with multiple recess portions in the particle containing metallic atom of metal portion, The sintered body of particle and metallic containing metallic atom becomes easier to contact, and mitigate the stress of connection structural bodies Effect improves.That is, being easier to cope with the particle containing metallic atom since the particle containing metallic atom has recess portion Deformation, as a result, even if applying stress to connection structural bodies being also more difficult to that warpage and crack occurs.

Preparing, there is the method for the substrate particle of recess portion to be not particularly limited.Such as by above-mentioned substrate particle carry out after Processing, can form recess portion in substrate particle.

Above by the forming method of recess portion of post-processing, there is no particular restriction, such as can use well known method.Tool For body, can enumerate: the method that is etched to the surface of substrate particle carries out at plasma in oxygen atmosphere Reason, ozone treatment and heat-treating methods, the method for humidification process carry out heat treatment method in a vacuum, are pressurizeing and adding Heat-treating methods are carried out under the conditions of wet, and the method for wet-treating is carried out with oxidant and is carried out at physics with ball mill etc. The method etc. of reason.

There is no particular restriction for the mean depth of recess portion.Such as the mean depth of recess portion can be the mean radius of substrate particle 0.1% or more and 80% or less.It should be noted that the depth of recess portion described herein refers to, in the base that will have recess portion In the case that material particle regards spherical shape as, the distance between the surface of the spherical shape substrate particle and the minimum point of recess portion.Specifically, With the measuring method same sequence of the average height with above-mentioned protrusion, by using the FE-SEM of embedded resin observe respectively with The protrusion of 20 particles containing metallic atom of machine selection, and the value that the depth of each recess portion progress arithmetic average is acquired.

Fig. 5 further illustrates the variation of the particle 10 containing metallic atom, and schematically shows that this contains metal The appearance of atomic particle.It should be noted that for the partial cross section structure for indicating the particle containing metallic atom, in Fig. 5, The fragmentary perspective that dotted line part is surrounded indicates.

Specifically, the particle 10 containing metallic atom of Fig. 5 has the substrate particle with multiple recess portions 14 and matches The metal portion 12 being placed on 11 surface of substrate particle, multiple protrusions 13 are formed on the outer surface of metal portion 12.12 shape of metal portion As the double-layer structure with the first metal portion 12a and the second metal portion 12b.That is, form shown in Fig. 5 containing metallic atom Particle 10 has the feature of both Fig. 3 and the particle 10 shown in Fig. 4 containing metallic atom.

In the case where the particle 10 containing metallic atom of form shown in Fig. 5, there are multiple protrusions 13, contain metal original The particle of son and the sintered body of metallic become easier to contact, further, since substrate particle 11 has multiple recess portions 14, because This is easy the deformation of particle of the reply containing metallic atom.Therefore, comprising containing metallic atom shown in form shown in Fig. 5 In the connection structural bodies of particle, it is particularly easy to inhibit generation and the crack of warpage.

For the particle 10 containing metallic atom of the form shown in Fig. 5, form shown in Fig. 3 containing metallic atom In particle 10, replaced using the substrate particle 11 with multiple recess portions 14 as substrate particle 11, other parts are in the same way It is made.

Unrelated with the form of particle 10 containing metallic atom, the hardness of the particle 10 containing metallic atom has no especially Limitation, such as 10%K value are 10N/mm²Above and 6000N/mm²Below.Just further inhibit connection structural bodies crack with And for the viewpoint of the generation of warpage, the 10%K value of the particle 10 containing metallic atom is preferably 100N/mm²More than, more preferably For 1000N/mm²More than, and preferably 5500N/mm²Hereinafter, particularly preferably 5000N/mm²Below.

There is no particular restriction for the metal contained in the sintered body of metallic.Such as institute in the sintered body of metallic The metal contained is preferably comprised selected from one or more of following compositions: gold, silver, tin, copper, germanium, indium, palladium, tellurium, thallium, bismuth, zinc, Arsenic, selenium and the alloy containing one or more of these metallic elements.In this case, the particle containing metallic atom becomes more It is easy and the sintered body of metallic contacts, generation and the crack of the warpage of connection structural bodies can be further suppressed.Clipped wire Metal contained by the sintered body of son, particularly preferably containing selected from one of gold, silver, copper.In addition, the sintering of metallic Body can be formed only by metal.

In adhesive layer, the particle containing metallic atom exists in the mode being embedded in the sintered body of metallic.Especially It is the particle containing metallic atom, exists in such a way that some or all of its surface is in contact with the sintered body of metallic.

Specifically, particle and sintered body containing metallic atom are contacted by chemical bond.The type of the chemical bond has no Limitation, can enumerate metallic bond.Contain in particular it is preferred that being present in the metal portion or protrusion on the surface of the particle containing metallic atom Some metals form solid solution with the metal contained in sintered body.In this case, particle and sintered body containing metallic atom It more firmly contacts, therefore, even if applying stress to connection structural bodies, is also more difficult to that warpage and crack occurs.

The surface of particle containing metallic atom can partially be in contact with sintered body, alternatively, the grain containing metallic atom The surface of son can also all be in contact with sintered body.

Specifically, in the connection structural bodies of present embodiment, in the section of adhesive layer, the grain containing metallic atom 5% or more of the outer perimeter of son is in contact with above-mentioned sintered body.The particle containing metallic atom connects securely with sintered body as a result, Touching even if applying stress to connection structural bodies is also more difficult to that warpage and crack occurs.

For the viewpoint of the surface area of the particle containing metallic atom, the total surface of the particle of metallic atom is preferably comprised Long-pending 5% or more is contacted with sintered body.

Fig. 6 schematically shows the cross section structure of the adhesive layer 50 in the connection structural bodies of present embodiment.Adhesive layer 50 has There are particle 10 and sintered body 20 containing metallic atom.Particle 10 containing metallic atom at least has substrate particle 11 and metal Portion 12 and formed.

In Fig. 6 (a), the major part of the outer perimeter of the particle 10 containing metallic atom, such as periphery overall length 5% with On, it is contacted with sintered body 20.Under the form, even if applying stress to connection structural bodies, also it is more difficult to that warpage and crack occurs.

On the one hand, in Fig. 6 (b), only a part of the outer perimeter of the particle 10 containing metallic atom, such as periphery overall length 5% hereinafter, being contacted with sintered body 20, a large amount of gap 9 is formed near the surface of the particle 10 containing metallic atom.At this Under form, if applying stress to connection structural bodies, the particle 10 containing metallic atom is deformed, then containing metallic atom Particle 10 restores to the power (restoring force) of original form to work.When being restored to original shape as described above, formed a large amount of Gap 9 and there are space, the restorative of particle is got higher, and due to the restoring force, constitutes adhesive layer or connection structural bodies other It is easy to produce crack in component parts, warpage occurs.

In the section of adhesive layer, preferably comprise the outer perimeter of the particle of metallic atom 10% or more connects with sintered body Touching, more preferably its 50% or more be in contact with sintered body, particularly preferably it 90% or more is in contact with sintered body.

For the periphery of the particle containing metallic atom on the section in adhesive layer is in contact with sintered body, such as can Confirmed with observation by transmission electron microscope FE-TEM.Such as it can confirm in the following way containing metallic atom Contact between particle and sintered body.

Firstly, adding the particle containing metallic atom into following sintering materials and making its dispersion, and make containing gold The content for belonging to atomic particle is 5 weight %, to prepare sintering paste (bonding composition).In addition, as the first connection Object Part, preparation are applied with the power semiconductor of Ni/Au plating on joint face.As the second connecting object component, system The standby aluminium nitride substrate that Cu plating is applied on joint face.On the second connecting object component, it is coated with above-mentioned sintering paste, and Make it with a thickness of about 70 μm, to form sintering paste layer.Then, on sintering paste layer, above-mentioned first connection pair of lamination As component, laminated body is obtained.

Then, obtained laminated body heating plate is preheated 60 seconds at 130 DEG C, then will be folded under the pressure of 10MPa Layer body heats 3 minutes at 300 DEG C, burns as a result, to the above-mentioned particle containing metallic atom contained by sintering paste Knot forms the interconnecting piece of the particle containing sinter and containing metallic atom, connects above-mentioned first, second by the sinter and connects Object Part is connect, connection structural bodies is obtained.

Then, obtained connection structural bodies is fitted into " Technovit4000 " of Kulzer company manufacture and is solidified, Prepare the embedded resin for detecting connection structural bodies.Using ion milling machine, (Hitachi High-Technologies Corporation is manufactured " IM4000 ") cut out the section of the particle containing metallic atom, and cut through disperse in the detection embedded resin contain metal The immediate vicinity of atomic particle.

Then, using transmission electron microscope FE-TEM (" JEM-2010FEF " anufactured by Japan Electron Optics Laboratory(JEOL)), lead to Energy dispersion type X-ray analyzer (EDS) is crossed, the part that the particle containing metallic atom is in contact with sintered body is carried out linear Analysis or element mapping, thus observe the disperse state of metal component.

By observing the disperse state of above-mentioned metal, it can be confirmed that the periphery of the particle containing metallic atom connects with sintered body The case where touching.

In addition, by the disperse state for mapping above-mentioned metal component, metal original can be contained by the calculatings such as calculating automatically Contact ratio between the periphery and sintered body of the particle of son, thus can also quantify contact ratio.

The sintered body of metallic, such as can be by being sintered the sintering material containing metallic at the specified temperature To be formed.

Metallic contained in sintering material can be the particle of metal simple-substance, be also possible to metallic compound Particle.Metallic compound is the compound of the atom containing metallic atom and in addition to metallic atom.

It as the specific example of metallic compound, can enumerate: metal oxide, metal carbonate, metal carboxylate and gold Belong to complex compound etc..Metallic compound is preferably metal oxide.Such as above-mentioned metal oxide leads in the presence of a reducing agent It crosses heating when connecting and becomes metallic, be then sintered.Above-mentioned metal oxide is the precursor of metallic.As metal Carboxylic acid salt particle can enumerate metal acetate particle etc..

Metal contained in metallic and metallic compound is preferably comprised selected from one or more of following compositions: gold, Silver, tin, copper, germanium, indium, palladium, tellurium, thallium, bismuth, zinc, arsenic, selenium and the alloy containing one or more of these metallic elements.? In this case, the sintered body of particle and metallic containing metallic atom is easier to contact, connection knot can be further suppressed The generation of the warpage of structure body and crack.Metal contained in the sintered body of metallic particularly preferably contain selected from gold, silver, One or more of copper.Using silver particles and oxidation silver particles, sintered body and the particle containing metallic atom More firmly contact.As silver oxide, Ag can be enumerated₂O and AgO.

The average grain diameter of metallic is preferably 10nm or more and 10 μm or less.In addition, just improving connecting object component For the viewpoint of adhesive strength, metallics preferably different with two or more average grain diameters.With two or more average In the case where the different metallic of partial size, the average grain diameter of the small metallic of average grain diameter is preferably 10nm or more, and Preferably 100nm or less.The average grain diameter of the big metallic of average grain diameter is preferably 1 μm or more, and preferably 10 μm with Under.The ratio between the combined amount of the small metallic of average grain diameter and the big combined amount of metallic of average grain diameter, preferably 1/9 Above and 9 or less.It should be noted that for above-mentioned average grain diameter, by observing metallic with scanning electron microscope, And arithmetic average is carried out to the maximum gauge of 50 optional each particles in observation image and is acquired.

Metallic is preferably sintered by the heating less than 400 DEG C.The temperature (sintering temperature) of metallic sintering is more Preferably 350 DEG C hereinafter, and preferably 300 DEG C or more.When above-mentioned metallic sintering temperature below the above-mentioned upper limit and When more than above-mentioned lower limit, sintering can be effectively performed, and the required energy of sintering can be reduced, mitigate carrying capacity of environment.

When metallic is metal oxide particle, the sintering material containing metallic preferably comprises reducing agent. As above-mentioned reducing agent, alcohols (compound with alcoholic extract hydroxyl group), carboxylic acids (compound with carboxyl), amine can be enumerated (compound with amino) etc..Above-mentioned reducing agent can be used only one kind, can also be applied in combination two or more.

As above-mentioned alcohols, alkylol can be enumerated.It as the specific example of above-mentioned alcohols, can enumerate: ethyl alcohol, propyl alcohol, fourth Alcohol, amylalcohol, hexanol, enanthol, octanol, nonyl alcohol, decyl alcohol, tip-nip, dodecanol, tridecanol, tetradecanol, pentadecane Alcohol, hexadecanol, heptadecanol, octadecanol, nonadecanol, eicosanol etc..In addition, being not limited to primary as above-mentioned alcohols The pure and mild alcoholic compound with cyclic structure of secondary alcohols, tert-alcohols, alkane two also can be used in alcoholic compound.In addition, As above-mentioned alcohols, the compound that ethylene glycol and triethylene glycol etc. have a large amount of alcohol radicals can be used.In addition, as above-mentioned alcohol The compounds such as citric acid, ascorbic acid and glucose can be used in class.

As above-mentioned carboxylic acids, alkyl carboxylic acid etc. can be enumerated.As the specific example of above-mentioned carboxylic acids, can enumerate: butyric acid, Valeric acid, caproic acid, enanthic acid, octanoic acid, n-nonanoic acid, capric acid, hendecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, ten Six alkanoic acids, Heptadecanoic acide, octadecanoid acid, nonadecylic acid and arachic acid etc..In addition, above-mentioned carboxylic acids is not limited to primary carboxylic acid chemical combination Secondary carboxylic ester compound, tertiary carboxylic acid compound, dicarboxylic acids and the carboxyl compound with cyclic structure also can be used in object.

As above-mentioned amine, alkylamine etc. can be enumerated.As the specific example of above-mentioned amine, can enumerate: butylamine, amylamine, Hexylamine, heptyl amice, octylame, nonyl amine, decyl amine, undecylamine, dodecyl amine, tridecyl amine, tetradecylamine, pentadecyl amine, cetylamine, ten Seven alkanamines, octadecylamine, nonadecane amine, dodecyl amine etc..In addition, above-mentioned amine can have branched structure.As with branch The amine of structure can enumerate 2 ethyl hexylamine and 1,5- dimethylhexylamine etc..Above-mentioned amine is not limited to primary amino-compound, can also be with Using secondary amine compound, tertiary amine compound and with the amine compounds of cyclic structure.

Above-mentioned reducing agent can be the organic matter with aldehyde radical, ester group, sulfonyl, ketone group etc., be also possible to carboxylic acid metal The organic matters such as salt.Carboxylic metallic salt can be used as the precursor of metallic, since it contains organic matter, it is also possible to make metal oxide The reducing agent of particle.

Relative to the metallic of 100 parts by weight, the content of above-mentioned reducing agent is preferably 1 parts by weight or more, more preferably It is more than 10 parts by weight, and preferably 1000 parts by weight hereinafter, more preferably 500 parts by weight hereinafter, further preferably 100 weights Measure part or less.When the content of above-mentioned reducing agent is more than above-mentioned lower limit, above-mentioned metallic can be sintered finer and close.

When being lower than the reducing agent of sintering temperature (connection temperature) of the above-mentioned particle containing metallic atom using fusing point, deposit It is easy cohesion when reducing agent is in connection, and is easy to produce the tendency in gap in interconnecting piece.By using carboxylic metallic salt, And the carboxylic metallic salt will not melt due to heating when connection, therefore can inhibit the generation in gap.It should be noted that In addition to carboxylic metallic salt, the metallic compound containing organic matter also is used as reducing agent.

Other materials may include in the sintering material containing metallic.It such as may include tree in sintering material Rouge ingredient.In the case where containing resin component, inhibit the generation in the crack of connection structural bodies, the generation of warpage and bonding The generation of the removing of layer.

Above-mentioned resin component is not particularly limited.Above-mentioned resin component preferably comprises thermoplastic resin or curable resin, Further preferably curable resin.As above-mentioned curable resin, light-cured resin and thermosetting resin can be enumerated.Above-mentioned light Curable resin preferably comprises light-cured resin and Photoepolymerizationinitiater initiater.Above-mentioned thermosetting resin preferably comprises thermosetting resin And thermal curing agents.As above-mentioned resin, such as well known vinylite, thermoplastic resin, curable resin, thermoplastic can be enumerated Property block copolymer and elastomer etc..Above-mentioned resin can be used only one kind, can also be applied in combination two or more.

In addition, may include decentralized medium in the sintering material containing metallic.As decentralized medium, such as can enumerate Well known solvent etc..

The above-mentioned sintering material containing metallic can be commercial product.As specific example, can enumerate KyoceraChemical Co., Ltd. manufacture " CT2700 ", Heraeus company manufacture " ASP295 ", " ASP016 ", " the H9890- that " the LOCTITE ABLESTIK SSP2020 " of the manufacture of " ASP043 ", Henkel company, Namics company manufacture " NH-4000 ", " NH-225D " that 6A ", Harima Co., Ltd. manufacture, the manufacture of " NH-3000D ", Kaken-tech Co., Ltd. " CM-3212 " and " CR-3520 ", NihonSuperior Co., Ltd. manufacture " Alconano Ag Paste ANP-1 " Deng.

In adhesive layer, the content of the particle containing metallic atom is preferably 0.1 weight % or more, more preferably 1 weight % or more is measured, and preferably 20 weight % are hereinafter, more preferably 10 weight % or less.When containing for the particle containing metallic atom When amount is more than above-mentioned lower limit and below the above-mentioned upper limit, the crack of connection structural bodies and the generation of warpage are further suppressed.

In adhesive layer, the preferred content of the metallic content that is greater than the above-mentioned particle containing metallic atom, such as more It is preferred that big 10 weight % or more, still more preferably big 20 weight % or more.

In adhesive layer, the content of metallic is preferably 70 weight % or more, more preferably 80 weight % or more, and Preferably 98 weight % are hereinafter, more preferably 95 weight % or less.When the content of the above-mentioned particle containing metallic atom is above-mentioned When more than lower limit and below the above-mentioned upper limit, the crack of connection structural bodies and the generation of warpage can be further suppressed.

There is no particular restriction for the manufacturing method of the connection structural bodies of present embodiment.Manufacture as above-mentioned connection structural bodies One example of method, can enumerate: between the first connecting object component and the second connecting object component, configuration is former containing metal The mixture that the particle and above-mentioned sintering material of son are formed is heated and is pressurizeed to the laminated body to form laminated body Method etc..The metallic contained in laminated body is sintered as a result, is formed in sintered body and is dispersed with containing metal original The adhesive layer of the particle of son, the first connecting object component and the second connecting object component realize connection by adhesive layer.

In particular, in the connection structural bodies of present embodiment, the surface of the particle containing metallic atom in adhesive layer It is most of to be contacted with the sintered body in adhesive layer, and its contact is relatively firm, and there is no need to installations of pressurizeing, in other words, can To be installed in the case where not applying pressure.Therefore, advantageously connection structural bodies can be manufactured in engineering.

The above-mentioned particle containing metallic atom, in the adhesive layer contained by connection structural bodies with the sintered body of metallic Contact area increase, therefore be suitable as the material for assembling above-mentioned connection structural bodies.Contain metal by above-mentioned as a result, Atomic particle can provide a kind of connection structural bodies for being difficult to happen warpage and crack.

In addition, the above-mentioned particle containing metallic atom is also applied for the constituent of bonding composition.Specifically, can The above-mentioned particle containing metallic atom and above-mentioned sintering metallic are combined to pass through, to prepare bonding composition.

Since above-mentioned bonding composition includes particle and metallic containing metallic atom, it is suitable as being used for The material of assembly and connection structural body.Specifically, by being applied between the first connecting object component and the second connecting object component Cloth bonding composition, the metallic in sinter bonded composition, it is possible thereby to be formed comprising the grain containing metallic atom The adhesive layer of son.

Above-mentioned bonding composition, can be by mixing particle and metal containing metallic atom according to the combined amount of regulation It is prepared by particle.For example, can by mixing the above-mentioned particle containing metallic atom and the sintering material containing metallic, To prepare bonding composition.The mixed method of particle and metallic containing metallic atom is not particularly limited, and can adopt With well known mixed method.

In bonding composition, the mixed proportion of particle and metallic containing metallic atom is not particularly limited.

For example, in the 100 weight % of ingredient in addition to decentralized medium of bonding composition, the grain containing metallic atom The content of son is preferably 0.1 weight % or more, more preferably 1 weight % or more, and preferably 20 weight % are hereinafter, more preferably 10 weight % or less.When the content of the above-mentioned particle containing metallic atom is more than above-mentioned lower limit and below the above-mentioned upper limit, on Stating metallic can be sintered finer and close, and the contact area of particle and sintered body containing metallic atom increases.

In addition, the content of metallic is excellent in the 100 weight % of ingredient in addition to decentralized medium of bonding composition Be selected as 70 weight % or more, more preferably 80 weight % or more, and preferably 98 weight % hereinafter, more preferable 95 weight % with Under.When the content of above-mentioned metallic is more than above-mentioned lower limit and below the above-mentioned upper limit, above-mentioned metallic can be sintered It is finer and close.

When above-mentioned bonding composition contains resin component, in the ingredient in addition to decentralized medium of bonding composition In 100 weight %, the content of above-mentioned resin component is preferably 1 weight % or more, more preferable 5 weight % or more, and preferably 20 Weight % is hereinafter, more preferable 15 weight % or less.When above-mentioned resin component content more than above-mentioned lower limit and the above-mentioned upper limit with When lower, above-mentioned metallic can be sintered finer and close.

Embodiment

Hereinafter, the present invention will be further illustrated by embodiment, but the embodiment party that the present invention is not limited to these Examples Formula.

(embodiment 1)

As substrate particle S1, divinyl benzene copolymer resin particle (the ponding chemical industry that partial size is 3.0 μm is prepared " the Micropearl SP-203 " of Co., Ltd.'s manufacture).

By ultrasonic dispersers by the substrate particle S1 of 10 parts by weight, it is scattered in the palladium containing 5 weight % of 100 parts by weight In the alkaline solution of catalyst solution, then filtering solution is to take out substrate particle S1.Then, substrate particle S1 is added to In the dimethylamine borane solution of 1 weight % of 100 parts by weight, with the surface of activated substrate particle S1.Abundant washing surface activation Substrate particle S1 after, be added into 500 parts by weight distilled water and make its dispersion, obtain suspension (A1).

Suspension (A1) is placed in the solution containing copper sulphate 20g/L and ethylenediamine tetra-acetic acid 30g/L, it is mixed to obtain particle It closes liquid (B1).

In addition, copper sulphate 250g/L, ethylenediamine tetra-acetic acid 150g/L, glucose will be contained as electroless plating copper solution The mixed liquor of sour sodium 100g/L and formaldehyde 50g/L is made, and the copper plating solution (C1) of pH 10.5 is adjusted to by ammonia.

In addition, silver nitrate 30g/L, succinimide 100g/L and formaldehyde 20g/L will be contained as electroless silver plating solution Mixed solution be made, the silver plating solution (D1) of pH 8.0 is adjusted to by ammonia.

Above-mentioned copper plating solution (C1) is gradually added drop-wise in the particle mixed liquor (B1) for the dispersity for being adjusted to 55 DEG C, and Carry out electroless copper facing.The condition that rate of addition with copper plating solution (C1) is 30mL/min, time for adding is 30 minutes carries out Electroless copper facing.In this manner, obtaining the particle mixed liquor (E1) containing following particle, which has on resin particle surface There is copper metal portion as the first metal portion.

Then, particle mixed liquor (E1) is filtered to take out particle and wash, to obtain on the surface of above-mentioned substrate particle S1 The upper particle configured with copper metal portion.After the particle is sufficiently washed, it is added in 500 parts by weight distilled water and makes its dispersion, Obtain particle mixed liquor (F1).

Then, above-mentioned silver plating solution (D1) is gradually added drop-wise to be adjusted to 60 DEG C dispersity particle mixed liquor (F1) In, carry out electroless silver plating.The condition that rate of addition with silver plating solution (D1) is 10mL/min, time for adding is 30 minutes, Carry out electroless silver plating.Then, particle, washing and drying are taken out by filtering, obtains having on the surface of substrate particle S1 The particle containing metallic atom of copper and silver metal portion (overall thickness of metal portion: 0.1 μm).

(embodiment 2)

Prepare the substrate particle S1 of embodiment 1.In addition, the identical suspension of suspension (A1) of preparation and embodiment 1 (A2)。

Then, by the metallic Ni particles slurry of 1 parts by weight, (Co., Ltd. of Mitsui Metal Co., Ltd. is manufactured in 3 minutes " 2020SUS ", average grain diameter 150nm) it is added in above-mentioned suspension (A2), it obtains containing the substrate particle S1 for being attached with core material Suspension (B2).

Suspension (B2) is added in the solution containing copper sulphate 20g/L and ethylenediamine tetra-acetic acid 30g/L, particle is obtained Mixed liquor (C2).

In addition, the identical copper plating solution (D2) of copper plating solution (C1) of preparation and embodiment 1.

In addition, the identical silver plating solution (E2) of silver plating solution (D1) of preparation and embodiment 1.

Then, above-mentioned copper plating solution (D2) is gradually added drop-wise to be adjusted to 55 DEG C dispersity particle mixed liquor (C2) In, carry out electroless copper facing.The condition that rate of addition with copper plating solution (D2) is 30mL/min, time for adding is 30 minutes, Carry out electroless copper facing.The particle mixed liquor (F2) containing following particle is obtained as a result, and the particle is on the surface of resin particle Configured with copper metal portion as the first metal portion, and has the metal portion that there is protrusion on surface.

Then, particle mixed liquor (F2) is filtered to take out particle and wash, to obtain on the surface of above-mentioned substrate particle S1 It is upper to be configured with copper metal portion, and have the particle of the metal portion with protrusion on the surface.After the particle is sufficiently washed, add Enter into 500 parts by weight distilled water and make its dispersion, obtains particle mixed liquor (G2).

Then, above-mentioned silver plating solution (E2) is gradually added drop-wise to be adjusted to 60 DEG C dispersity particle mixed liquor (G2) In, and carry out electroless silver plating.The item that rate of addition with silver plating solution (E2) is 10mL/min, time for adding is 30 minutes Part carries out electroless silver plating.Then, particle is taken out by filtering, washes and dry, obtains grain as follows containing metallic atom Son, the particle on the surface of substrate particle S1 configured with copper and silver metal portion (the not no metal portion overall thickness of the part of protrusion: 0.1 μm), and have metal portion on the surface with multiple protrusions.

(embodiment 3)

Other than metallic Ni particles slurry to be become to aluminium oxide particles slurry (average grain diameter: 150nm), with embodiment Identical mode obtains the particle containing metallic atom in 2.

(embodiment 4)

Other than metallic Ni particles slurry to be become to copper particle slurry (average grain diameter: 150nm), with in embodiment 2 Identical mode obtains the particle containing metallic atom.

(embodiment 5)

Suspension obtained in embodiment 1 (A1) is put into containing nickel sulfate 40ppm, trisodium citrate 2g/L and ammonia 10g/ In the solution of L, particle mixed liquor (B5) is obtained.

As the plating solution for being used to form nadel, copper sulphate 100g/L, nickel sulfate 10g/L, ortho phosphorous acid will be contained The polyethylene glycol of sodium 100g/L, trisodium citrate 70g/L, boric acid 10g/L and the 5mg/L as nonionic surface active agent 1000 (molecular weight: mixed liquor 1000) is made, and electrolytic copper free-nickel-phosphor alloy plating solution of pH 10.0 is adjusted to by ammonia, It is used to form the plating solution (C5) of nadel.

In addition, silver nitrate 30g/L, succinimide 100g/L and formaldehyde 20g/L are formed as electroless silver plating solution Mixed liquor be made, the silver plating solution (D5) of pH 8.0 is adjusted to by ammonia.

The above-mentioned plating solution (C5) for being used to form nadel is gradually added drop-wise to be adjusted to 70 DEG C dispersity grain In sub- mixed liquor (B5), nadel is formed.Be used to form nadel plating solution (C5) rate of addition be 40mL/ Min, the condition that time for adding is 60 minutes, carry out electrolytic copper free-nickel-phosphor alloy plating and (form nadel and Cu-Ni-P Alloy plated process).Then, particle is taken out by filtering, obtains following particles (E5), the particle (E5) is substrate particle S1's It is configured with Cu-Ni-P alloying metal portion on surface, and has the metal portion on the surface with protrusion (protrusion is precipitated).It will Particle (E5) is added in the distilled water of 500 parts by weight and makes its dispersion, to obtain suspension (F5).

Then, suspension (F5) is filtered to take out particle and wash, and to obtain following particles, the particle is in above-mentioned substrate It is configured with Cu-Ni-P alloying metal portion on the surface of particle A, and has metal portion on the surface with needle-shaped protrusion.It is right After the particle water is sufficiently washed, it is added in 500 parts by weight distilled water and is made its dispersion, obtains particle mixed liquor (G5).

Then, above-mentioned silver plating solution (D5) is gradually added drop-wise to be adjusted to 60 DEG C dispersity particle mixed liquor (G5) In, carry out electroless silver plating.The condition that rate of addition with silver plating solution (D5) is 10mL/min, time for adding is 30 minutes, Carry out electroless silver plating.Then, particle is taken out by filtering, washed and dry, to obtain following particles containing metallic atom, The particle is configured with Cu-Ni-P alloy portion and silver metal portion (the not metal of the part of protrusion on the surface of substrate particle S1 Portion's overall thickness: 0.1 μm), and have metal portion on the surface with multiple nadels.

(embodiment 6)

Suspension obtained in embodiment 1 (A1) is put into containing potassium cyanide silver 500ppm, potassium cyanide 10g/L and hydroxide In the solution of potassium 10g/L, particle mixed liquor (B6) is obtained.

As the plating solution for being used to form nadel, potassium cyanide silver 80g/L, potassium cyanide 10g/L, polyethylene glycol will be contained 1000 (molecular weight: 1000) mixed liquor of 20mg/L, thiocarbamide 50ppm and a hydrazine hydrate 100g/L are made, by potassium hydroxide tune Section is the silver plating solution (C6) of pH 7.5.

Above-mentioned electroless silver plating solution (C6) is gradually added drop-wise to be adjusted to 80 DEG C dispersity particle mixed liquor (B6) in, nadel is formed.Rate of addition with electroless silver plating solution (C6) is 10mL/min, time for adding is 60 minutes Condition, carry out electroless silver plating (formed nadel and silver-plated process).Then, particle taken out by filtering, washed and done Dry, to obtain following particles containing metallic atom, which (does not dash forward on the surface of resin particle configured with silver metal portion The metal portion overall thickness for the part risen: 0.1 μm), and have the silver metal portion for being formed with multiple nadels on the surface.

(embodiment 7)

Suspension obtained in embodiment 2 (B2) addition is contained copper sulphate 20g/L's and ethylenediamine tetra-acetic acid 30g/L In solution, particle mixed liquor (C7) is obtained.

In addition, copper sulphate 300g/L, ethylenediamine tetra-acetic acid 150g/L, glucose will be contained as electroless plating copper solution The mixed liquor of sour sodium 120g/L and formaldehyde 70g/L is made, and the copper plating solution (D7) of pH 10.5 is adjusted to by ammonia.

Then, above-mentioned copper plating solution (D7) is gradually added drop-wise to be adjusted to 55 DEG C dispersity particle mixed liquor (C7) In, carry out electroless copper facing.Rate of addition with copper plating solution (D7) is 30mL/min, time for adding is 30 minutes, carries out nothing Electrolytic copper plating.Then, particle is taken out by filtering, obtains the particle mixed liquor (F7) containing following particle as a result, which exists It is configured with copper metal portion on the surface of substrate particle A, and has metal portion on the surface with protrusion.

Then, particle, washing and drying are taken out by filtering, obtains following particles containing metallic atom, which exists Configured with copper metal portion (not the metal portion overall thickness of the part of protrusion: 0.1 μm) on the surface of substrate particle A, and have On the surface with the metal portion of multiple protrusions.

(embodiment 8)

Suspension obtained in embodiment 2 (B2) addition is contained into the molten of copper sulphate 20g/L and ethylenediamine tetra-acetic acid 30g/L In liquid, particle mixed liquor (C8) is obtained.

In addition, copper sulphate 250g/L, ethylenediamine tetra-acetic acid 150g/L, glucose will be contained as electroless plating copper solution The mixed solution of sour sodium 100g/L and formaldehyde 50g/L is made, and the copper plating solution (D8) of pH 10.5 is adjusted to by ammonia.

In addition, as electroless plating solution of tin, will containing stannic chloride 20g/L, nitrilotriacetic acid 50g/L, thiocarbamide 2g/L, The mixed liquor of thiomalic acid 1g/L, ethylenediamine tetra-acetic acid 7.5g/L and titanium trichloride 15g/L are made, and are adjusted to pH by sulfuric acid 7.0 tin plating solution (E8).

Then, above-mentioned copper plating solution (D8) is gradually added drop-wise to be adjusted to 55 DEG C dispersity particle mixed liquor (C8) In, carry out electroless copper facing.The condition that rate of addition with copper plating solution (D8) is 30mL/min, time for adding is 30 minutes, Carry out electroless copper facing.Then, particle is taken out by filtering, obtains the particle mixed liquor (F8) containing following particle as a result, it should Particle is configured with copper metal portion on the surface of substrate particle A, and has metal portion on the surface with protrusion.

Then, particle, washing and drying are taken out by filtering particle mixed liquor (F8), obtains following particle, which exists It is configured with copper metal portion on the surface of above-mentioned substrate particle A, and has metal portion on the surface with protrusion.To the particle Sufficiently after washing, it is added into 500 parts by weight distilled water and makes its dispersion, obtain particle mixed liquor (G8).

Then, above-mentioned tin plating solution (E8) is gradually added drop-wise to be adjusted to 60 DEG C dispersity particle mixed liquor (G8) In, it carries out electroless tin plating.The condition that rate of addition with tin plating solution (E8) is 10mL/min, time for adding is 30 minutes, It carries out electroless tin plating.Then, particle is taken out by filtering, washes and dry, obtains following particle, the particle is in substrate particle Configured with copper and tin metal portion (not the metal portion overall thickness of the part of protrusion: 0.1 μm) on the surface of A, and have in table Face has the metal portion of multiple protrusions.

(embodiment 9)

Suspension obtained in embodiment 1 (A1) investment is contained into nickel sulfate 25g/L, thallium nitrate 15ppm and bismuth nitrate In the solution of 10ppm, particle mixed liquor (B9) is obtained.

In addition, preparation containing nickel sulfate 100g/L, sodium hypophosphite 40g/L, sodium citrate 15g/L, thallium nitrate 25ppm, The nickel plating solution (C9) (pH 5.5) of bismuth nitrate 10ppm.

In addition, preparation contains gold potassium cyanide 10g/L, sodium citrate 20g/L, ethylenediamine tetra-acetic acid 3.0g/L and sodium hydroxide The gold plating solution (D9) (pH 9.0) of 20g/L.

Then, above-mentioned nickel plating solution (C9) is gradually added drop-wise to be adjusted to 50 DEG C dispersity particle mixed liquor (B9) In, carry out electroless nickel plating.The item that rate of addition with nickel plating solution (C8) is 12.5mL/min, time for adding is 30 minutes Part carries out electroless nickel plating (nickel plating process).The particle mixed liquor (E9) containing following particles is obtained as a result, which is setting The surface of fat granule has nickel metal portion as the first metal portion.

Then, particle, washing are taken out by filtering particle mixed liquor (E9), obtained on the surface of above-mentioned substrate particle A Particle configured with nickel metal portion.The particle is carried out after sufficiently washing, is added to 500 parts by weight distilled water, is made its dispersion, obtain To particle mixed liquor (F9).

Then, above-mentioned gold plating solution (D9) is gradually added drop-wise to be adjusted to 60 DEG C dispersity particle mixed liquor (F9) In, carry out electroless gold plating.The condition that rate of addition with gold plating solution (D8) is 2mL/min, time for adding is 45 minutes, into Row electroless gold plating.Then, particle, washing and drying are taken out by filtering, obtains following particles containing metallic atom, the grain Son has nickel and golden metal portion (metal portion overall thickness: 0.05 μm) on the surface of substrate particle A.

(embodiment 10)

Prepare the substrate particle S1 of embodiment 1.100 are dispersed by the substrate particle S1 of 10 parts by weight by ultrasonic dispersers In the alkaline solution containing 10 weight % potassium permanganate of parts by weight, then filtering solution is to take out substrate particle S1.Substrate grain Recess portion is formed on the surface of sub- S1.

Then, by ultrasonic dispersers by the substrate particle S1 of 10 parts by weight be scattered in 100 parts by weight containing 5 weight % In the alkaline solution of palladium catalyst solution, then filtering solution is to take out substrate particle S1.Then, substrate particle S1 is added In the dimethyamine borane solution of 1 weight % of 100 parts by weight, so that the surface active of substrate particle S1.In sufficiently washing table After the substrate particle A that face has activated, it is added into the distilled water of 500 parts by weight, is dispersed, obtain suspension (A10).In reality It applies in example 1, other than using suspension (A10) to replace suspension (A1), is obtained in the same manner as example 1 containing gold Belong to atomic particle.

(embodiment 11)

Then, by ultrasonic dispersers by the substrate particle S1 of 10 parts by weight be scattered in 100 parts by weight containing 5 weight % In the alkaline solution of palladium catalyst solution, then filtering solution is to take out substrate particle S1.Then, substrate particle S1 is added In the dimethyamine borane solution of 1 weight % of 100 parts by weight, so that the surface active of substrate particle S1.Sufficiently washing surface It after the substrate particle A activated, is added into the distilled water of 500 parts by weight, is dispersed, obtain suspension (A11).

Then, metallic Ni particles slurry (Mitsui Metal Co., Ltd. of 1 parts by weight is added into above-mentioned suspension (A11) in 3 minutes " 2020SUS " of Co., Ltd.'s manufacture, average grain diameter 150nm), the suspension (B11) containing substrate particle A is obtained, core material is attached In substrate particle A.

Suspension (B11) is added in the solution containing copper sulphate 5g/L and ethylenediamine tetra-acetic acid 8g/L, particle is obtained Mixed liquor (C11).

In addition, copper sulphate 50g/L, ethylenediamine tetra-acetic acid 30g/L, gluconic acid will be contained as electroless plating copper solution The mixed solution of sodium 20g/L and formaldehyde 10g/L are made, and the copper plating solution (D11) of pH 10.5 is adjusted to by ammonia.

In addition, silver nitrate 6g/L, succinimide 20g/L and formaldehyde 5g/L will be contained as electroless silver plating solution Mixed liquor be made, the silver plating solution (E11) of pH 8.0 is adjusted to by ammonia.

Then, above-mentioned copper plating solution (D11) is gradually added drop-wise to be adjusted to 55 DEG C dispersity particle mixed liquor (C11) in, electroless copper facing is carried out.Rate of addition with copper plating solution (D11) is 5mL/min, time for adding is 40 minutes Condition carries out electroless copper facing.The particle mixed liquor (F11) containing following particles is obtained as a result, and the particle is in resin particle Configured with copper metal portion as the first metal portion on surface, and has the metal portion that there is protrusion on surface.

Then, particle is taken out by filtering particle mixed liquor (F11), washes and dry, obtains following particles, which exists It is configured with copper metal portion on the surface of above-mentioned substrate particle S1, and has the metal portion that there is protrusion on surface.To the particle Sufficiently after washing, it is added into 500 parts by weight distilled water, and make its dispersion, obtains particle mixed liquor (G11).

Then, above-mentioned silver plating solution (E11) is gradually added drop-wise to be adjusted to 60 DEG C dispersity particle mixed liquor (G11) in, electroless silver plating is carried out.Rate of addition with silver plating solution (E11) is 5mL/min, time for adding is 15 minutes Condition carries out electroless silver plating.Then, particle is taken out by filtering, washes and dry, obtains following grains containing metallic atom Son, the particle are configured with recess portion, copper and silver metal portion (the not metal portion total thickness of protrusion on the surface of substrate particle S1 Degree: 0.01 μm), and have the metal portion that there are multiple protrusions on surface.

(embodiment 12)

Prepare the substrate particle S1 of embodiment 1.100 are dispersed by the substrate particle S1 of 10 parts by weight by ultrasonic dispersers In the alkaline solution containing 10 weight % potassium chromates of parts by weight, then filtering solution is to take out substrate particle S1.Substrate particle There is recess portion on the surface of S1.

Then, by ultrasonic dispersers by the substrate particle S1 of 10 parts by weight be scattered in 100 parts by weight containing 5 weight % In the alkaline solution of palladium catalyst solution, then filtering solution is to take out substrate particle S1.Then, substrate particle S1 is added In the dimethyamine borane solution of 1 weight % of 100 parts by weight, so that the surface active of substrate particle S1.Sufficiently washing surface It after the substrate particle A activated, is added into 500 parts by weight distilled water, is dispersed, obtain suspension (A12).

Then, 1 part by weight of metal nickel particles slurry of addition (Mitsui Metal Co., Ltd.'s strain into above-mentioned suspension (A12) in 3 minutes " 2020SUS " of formula commercial firm manufacture, average grain diameter 150nm), obtain the suspension (B12) containing substrate particle A, core material attachment In substrate particle A.

Other than using suspension (B12) to replace the suspension (B2) in embodiment 2, with side same as Example 2 Formula obtains the particle containing metallic atom.

(embodiment 13)

1. the preparation of siloxane oligomer

Into the removable flask of 100ml being placed in warm bath slot, 1,3- divinyl tetramethyl, two silicon of 1 parts by weight is added The p-methyl benzenesulfonic acid aqueous solution of oxygen alkane and 0.5 weight % of 20 parts by weight.After stirring 1 hour at 40 DEG C, 0.05 weight is added The sodium bicarbonate of part.Then, the dimethoxymethylphenylsilane of 10 parts by weight, the dimethylformamide dimethyl oxygroup of 49 parts by weight are added The methyltrimethoxysilane of silane, the trimethylmethoxysilane of 0.6 parts by weight and 3.6 parts by weight, and stir 1 hour.So Afterwards, the potassium hydroxide aqueous solution for adding 10 weight % of 1.9 parts by weight, raises the temperature to 85 DEG C, and reduce with aspirator It stirs 10 hours, is reacted while pressure.After the completion of reaction, by pressure recovery to normal pressure, 40 DEG C are cooled to, addition The acetic acid of 0.2 parts by weight stands 12 hours or more in separatory funnel.Lower layer will be taken out after two separate, is purified with evaporator, Obtain siloxane oligomer.

2. the preparation of Silicone particles material (including organic polymer)

By the t-butyl peroxy of 0.5 parts by weight -2 ethyl hexanoic acid ester, (polymerization initiator, Japan Oil Co are manufactured " PERBUTYL O ") it is dissolved in the resulting siloxane oligomer of 30 parts by weight, to prepare solution A.In addition, in 150 parts by weight Ion exchange water in, mix 0.8 parts by weight 40 weight % triethanolamine dodecylbenzene base sulfate (emulsifier) it is water-soluble Liquid, with the polyvinyl alcohol of 5 weight % of 80 parts by weight (degree of polymerization: about 2000, saponification degree: 86.5~89 moles of %, Japan's synthesis Chemical Co., Ltd. manufacture " Gohsenol GH-20 ") aqueous solution, to prepare aqueous solution B.To be set in warm bath slot can It tears open in formula flask, adds above-mentioned solution A, then add above-mentioned aqueous solution B.Then, using Shirasu Porous Glass (SPG) film (about 1 μm of the equal diameter in hole) is emulsified.Then, temperature is risen to 85 DEG C, and carries out polymerization 9 hours.After polymerization All particles are washed and are freeze-dried by centrifuge separation.It after drying, is crushed by ball mill, until the cohesion of particle Body reaches the ratio (average aggregate particle size/average primary particle diameter) of target, obtains the Silicone particles (base that partial size is 3.0 μm Material particle S2).

Other than above-mentioned substrate particle S1 is changed to above-mentioned substrate particle S2, shape in the same way as in example 2 At metal portion, the particle containing metallic atom is obtained.

(embodiment 14)

In addition to using two terminal acrylic acid silicone oil (" X-22-2445 " of Shin-Etsu Chemial Co., Ltd's manufacture) to replace silicon Except oxygen alkane oligomer, the Silicone particles (substrate particle that partial size is 3.0 μm is obtained in a manner of identical with embodiment 13 S3)。

Other than above-mentioned substrate particle S1 is changed to above-mentioned substrate particle S3, shape in the same way as in example 2 At metal portion, the particle containing metallic atom is obtained.

(embodiment 15)

Only the partial size substrate particle S4 different from substrate particle S1, partial size are 2.0 μm for preparation.

Other than above-mentioned substrate particle S1 is changed to above-mentioned substrate particle S4, shape in the same way as in example 2 At metal portion, the particle containing metallic atom is obtained.

(embodiment 16)

Only the partial size substrate particle S5 different from substrate particle S1, partial size are 10.0 μm for preparation.

Other than above-mentioned substrate particle S1 is changed to above-mentioned substrate particle S5, shape in the same way as in example 2 At metal portion, the particle containing metallic atom is obtained.

(embodiment 17)

Only the partial size substrate particle S6 different from substrate particle S1, partial size are 35.0 μm for preparation.

Other than above-mentioned substrate particle S1 is changed to above-mentioned substrate particle S6, shape in the same manner as example 1 At metal portion, the particle containing metallic atom is obtained.

(embodiment 18)

Other than above-mentioned substrate particle S1 to be changed to the above-mentioned substrate particle S6 of embodiment 17, with 8 phase of embodiment Same mode forms metal portion, obtains the particle containing metallic atom.

(embodiment 19)

By 100g ethylene glycol dimethacrylate, 800g isobornyl acrylate, 100g cyclohexyl methacrylate and The mixing of 35g benzoyl peroxide and uniform dissolution, obtain monomer mixed solution.Prepare the water-soluble of the 1 weight % of polyvinyl alcohol of 5kg Liquid adds it in reaction kettle.Above-mentioned monomer mixture is added thereto, stirs 2~4 hours to adjust partial size, and make The drop of monomer has defined partial size.Then, it is reacted 9 hours under 90 DEG C of nitrogen atmosphere, to obtain particle.It will be resulting After particle is washed for several times with hot water, progressive operation is carried out, obtains the substrate particle S7 that average grain diameter is 35.0 μm.

Other than above-mentioned substrate particle S1 is changed to above-mentioned substrate particle S7, shape in the same manner as example 1 At metal portion, the particle containing metallic atom is obtained.

(embodiment 20)

Other than above-mentioned substrate particle S1 is changed to the substrate particle S7 of embodiment 19, with same as Example 9 Mode forms metal portion, obtains the particle containing metallic atom.

(embodiment 21)

Only the partial size substrate particle S8 different from the substrate particle S7 of embodiment 19, partial size are 50.0 μm for preparation.In addition to Above-mentioned substrate particle S7 is changed to except above-mentioned substrate particle S8, metal portion is formed in the same manner as example 1, obtains Particle containing metallic atom.

(comparative example 1)

(comparative example 2)

By ultrasonic dispersers by the above-mentioned substrate particle S1 of 10 parts by weight be scattered in 100 parts by weight containing 5 weight % Palladium catalyst solution alkaline solution in, then filtering solution is to take out substrate particle S1.Then, substrate particle S1 is added Into the dimethylamine borane solution of 1 weight % of 100 parts by weight, with the surface of activated substrate particle S1.Abundant washing surface is living After the substrate particle S1 changed, its dispersion is added it in 500 parts by weight distilled water and made, obtains suspension (a1).

Suspension (a1) is added in the solution containing nickel sulfate 50g/L, thallium nitrate 30ppm and bismuth nitrate 20ppm, is obtained To particle mixed liquor (b1).

Then, preparation containing nickel sulfate 200g/L, sodium hypophosphite 85g/L, sodium citrate 30g/L, thallium nitrate 50ppm and The nickel plating solution (c1) (pH 6.5) of bismuth nitrate 20ppm.

Then, above-mentioned nickel plating solution (c1) is gradually added drop-wise to be adjusted to 50 DEG C dispersity particle mixed liquor (b1) In, carry out electroless nickel plating.The condition that rate of addition with nickel plating solution (c1) is 25mL/min, time for adding is 60 minutes, It carries out electroless nickel plating (nickel plating process).Then, particle is taken out by filtering, washed and dry, obtain containing metal original as follows The particle (metal portion overall thickness: 0.1 μm) of son, the particle are configured with nickel-phosphor metal portion on the surface of substrate particle S1, and Has the metal portion that there is protrusion on surface.

(comparative example 3)

Then, by 1g metallic Ni particles slurry, (" 2020SUS " of Co., Ltd. of Mitsui Metal Co., Ltd. manufacture, is averaged in 3 minutes Partial size 150nm) it is added in suspension (a1) identical with comparative example 1, the suspension (b2) containing substrate particle S1 is obtained, it should Core material is attached on substrate particle S1.

Suspension (b2) is added in the solution containing nickel sulfate 50g/L, thallium nitrate 30ppm and bismuth nitrate 20ppm, Obtain particle mixed liquor (c2).

Then, preparation containing nickel sulfate 200g/L, sodium hypophosphite 85g/L, sodium citrate 30g/L, nitric acid 50ppm thallium and The nickel plating bath (d2) (pH 6.5) of bismuth nitrate 20ppm.

Then, above-mentioned nickel plating solution (d2) is gradually added drop-wise to be adjusted to 50 DEG C dispersity particle mixed liquor (c2) In, carry out electroless nickel plating.The condition that rate of addition with nickel plating solution (d2) is 25mL/min, time for adding is 60 minutes, It carries out electroless nickel plating (nickel plating process).Then, particle is taken out by filtering, washed and dry, obtained following containing metal original The particle (metal portion overall thickness: 0.1 μm) of son, the particle are configured with nickel-phosphor metal portion on the surface of substrate particle A, and Has the metal portion that there is protrusion on surface.

(evaluation method)

1. the measurement of rising height

The obtained particle containing metallic atom is added in " Technovit4000 " of Kulzer company manufacture, is made The content for obtaining the particle containing metallic atom is 30 weight % and makes its dispersion, with preparation for detecting the grain containing metallic atom The embedded resin of son.It is cut out using ion milling machine (" IM4000 " of Hitachi High-Technologies Corporation manufacture) containing metallic atom Particle section, and cut through the immediate vicinity of the particle containing metallic atom dispersed in the detection embedded resin.

It then, will using transmission electron microscope FE-TEM (" JEM-ARM200F " anufactured by Japan Electron Optics Laboratory(JEOL)) Image multiplying power is set as 50,000 times, randomly choose 20 particles containing metallic atom, each particle containing metallic atom of observation Protrusion.The height for measuring the protrusion in the resulting particle containing metallic atom carries out arithmetic average to it to obtain protrusion Average height.

(2) measurement of the average diameter of the base portion of protrusion

The obtained particle containing metallic atom is added in " Technovit4000 " of Kulzer company manufacture, is made The content of the obtained particle containing metallic atom is 30 weight % and makes its dispersion, contains metallic atom for detecting with preparation Particle embedded resin.It is cut out using ion milling machine (" IM4000 " of Hitachi High-Technologies Corporation manufacture) containing metal The section of atomic particle, and cut through the immediate vicinity of the particle containing metallic atom dispersed in the detection embedded resin.

It then, will using transmission electron microscope FE-TEM (" JEM-ARM200F " anufactured by Japan Electron Optics Laboratory(JEOL)) Image multiplying power is set as 50,000 times, randomly choose 20 particles containing metallic atom, each particle containing metallic atom of observation Protrusion.The base diameter of protrusion in particle of the measurement gained containing metallic atom, carries out arithmetic average to it to obtain protrusion Base portion average diameter.

(3) shape of protrusion is observed

Then, using scanning electron microscope (FE-SEM), image multiplying power is set as 25000 times, randomly chooses 20 Particle containing metallic atom observes the protrusion of the respectively particle containing metallic atom, investigates the type of the affiliated shape of all protrusions.

(4) overall thickness of the not metal portion of protrusion is measured

It then, will using transmission electron microscope FE-TEM (" JEM-ARM200F " anufactured by Japan Electron Optics Laboratory(JEOL)) Image multiplying power is set as 50,000 times, randomly chooses 20 particles containing metallic atom, observation respectively containing metallic atom without protrusion Partial metal portion.The overall thickness for not having the metal portion of protrusion in the resulting particle containing metallic atom is measured, and right It carries out arithmetic average to obtain the overall thickness of the not metal portion of protrusion.

(4-1) measures occupied area ratio of the protrusion relative to the particle area containing metallic atom

Using scanning electron microscope (FE-SEM), image multiplying power is set as 6000 times, random selection 20 contain gold Belong to atomic particle, shoots respectively containing the particle of metallic atom.Then, FE-SEM figure is analyzed by commercially available image analysis software Picture.

After the image procossings such as being planarized, the area of protrusion is acquired, contains metallic atom for 20 Particle finds out ratio of the area of protrusion relative to the particle area containing metallic atom, using its average value as occupying Area ratio.

(5) in metal portion entirety nickel average content

The particle that 5g is contained to metallic atom, the mixing that 37% hydrochloric acid of 60% nitric acid and 10mL that are added to 5mL is formed In solution, it is completely dissolved conductive layer, obtains solution.Using obtained solution, pass through (the Hitachi's strain of ICP-MS analyzer Formula commercial firm manufacture) analysis nickel content.

(6) depth of the recess portion of the surface portion of substrate particle is measured

The obtained particle containing metallic atom is added in " Technovit4000 " of Kulzer company manufacture, is made The content of the obtained particle containing metallic atom is 30 weight % and makes its dispersion, contains metallic atom for detecting with preparation Particle embedded resin.It is cut out using ion milling machine (IM4000 " of Hitachi High-Technologies Corporation manufacture) containing metal The section of atomic particle, and cut through the immediate vicinity of the particle containing metallic atom dispersed in the detection embedded resin.

Then, using transmission electron microscope (FE-TEM) (" JEM-ARM200F " anufactured by Japan Electron Optics Laboratory(JEOL)), Image multiplying power is set as 50,000 times, randomly chooses 50 particles containing metallic atom, is observed respectively containing the surface element of metallic atom The recess portion divided.The depth of the recess portion of the surface portion of the substrate particle of the resulting particle containing metallic atom is measured, and to it Arithmetic average is carried out to obtain the depth of the recess portion of substrate particle surface portion.

(7) modulus of elasticity in comperssion (10%K value) of the particle containing metallic atom

For the above-mentioned modulus of elasticity in comperssion (10%K value) of the obtained particle containing metallic atom, in 23 DEG C of item Under part, using micro- compressing tester (" the Fischer Scope H-100 " of the manufacture of Fischer company) measurement, 10%K is acquired Value.

(8) peripheral part of the particle containing metallic atom in the connection structural bodies A1 in measurement pressurization installation and above-mentioned burning Contact ratio between knot body

The obtained particle containing metallic atom is added to standby " the ANP-1 " (silver paste of NihonSuperior corporation Material) and make its dispersion, and make the 5 weight % of content of the particle containing metallic atom, prepare (the engagement combination of sintering paste Object).

As the first connecting object component, preparation is coated with the power semiconductor of Ni/Au in connection table.As second Connecting object component, preparation are coated with the power semiconductor of Cu on joint face.

Above-mentioned sintering paste is coated on the second connecting object component, and makes about 70 μm of its thickness, forms sintering Paste layer.Then, on sintering paste layer, the above-mentioned first connecting object component of lamination obtains laminated body.

Obtained laminated body is preheated 60 seconds on 130 DEG C of hot plate, then laminated body exists under the pressure of 10MPa It heats 3 minutes, the above-mentioned particle containing metallic atom contained in sintering paste is sintered as a result, with shape at 300 DEG C At the interconnecting piece of the particle containing sinter and containing metallic atom, above-mentioned first and second connection pair is connected by the sinter As component, connection structural bodies A1 is obtained.

Then, obtained connection structural bodies A1 is added in " Technovit4000 " of Kulzer company manufacture keeps it solid Change, manufactures the embedded resin for checking connection structural bodies.Using ion milling machine, (Hitachi High-Technologies Corporation is manufactured " IM4000 ") section of the particle containing metallic atom is cut out, and cut through the connection structural bodies A1 in the detection embedded resin Immediate vicinity.

Using transmission electron microscope FE-TEM (" JEM-2010FEF " anufactured by Japan Electron Optics Laboratory(JEOL)), pass through energy Chromatic dispersion quantity type X-ray analyzer (" EX-470 " that hole field makes the manufacture of Co., Ltd. of institute), to the particle containing metallic atom and The contact portion of sintered body carries out element mapping, to observe the disperse state of metal.

By mapping the disperse state of above-mentioned metal, the periphery of the above-mentioned particle containing metallic atom of calculating and above-mentioned sintering Contact ratio between body.

[judgment criteria of contact ratio]

000: contact ratio is more than 80% and is 100% or less.

00: contact ratio is more than 50% and is 80% or less.

Zero: contact ratio is more than 30% and is 50% or less.

△: contact ratio is 5% or more and is 30% or less.

×: contact ratio is less than 5%.

(9) flatness of the power semiconductor in connection structural bodies A1

By the flatness of the power semiconductor of connection structural bodies A1 obtained in the evaluation of above-mentioned (8), by high-precision Spend laser displacement gauge (" LK-G5000 " of the manufacture of Keyence Co., Ltd.) measurement maximum displacement and maximum displacement.According to Obtained measured value determines above-mentioned flatness by following equation.

Flatness (μm)=maximum displacement (μm)-least displacement (μm)

[judgment criteria of flatness]

000: flatness is 0.5 μm or less.

00: flatness is more than 0.5 μm and is 1 μm or less.

Zero: flatness is more than 1 μm and is 5 μm or less.

△: flatness is more than 5 μm and is 10 μm or less.

×: flatness is more than 10 μm.

(10) connection reliability in connection structural bodies A1

Connection structural bodies A1 obtained in the evaluation of above-mentioned (8) is packed into cold-hot impact tester (ESPEC Co. Ltd. system " TSA-101S-W " made) in, by -40 DEG C of minimum temperature the retention time be 30 minutes, the guarantor at 200 DEG C of maximum temperature It holds the treatment conditions that the time is 30 minutes to recycle as one, after 3000 circulations, with (RHESCA plants of shear strength test instrument " STR-1000 " of formula commercial firm manufacture) measurement adhesive strength.

[judgment criteria of connection reliability]

000: adhesive strength is more than 50MPa.

00: adhesive strength is more than 40MPa and is less than 50MPa.

Zero: adhesive strength is more than 30MPa and is less than 40MPa.

△: adhesive strength is more than 20MPa and is less than 30MPa.

×: adhesive strength is less than 20MPa.

(11) measure the peripheral part of the particle containing metallic atom in non-pressurised installation in connection structural bodies A2 with it is above-mentioned Contact ratio between sintered body

The obtained particle containing metallic atom is added to " ANP-1 " (silver of NihonSuperior Co., Ltd. preparation Paste) in make its dispersion, and make the 5 weight % of content of the particle containing metallic atom, (engagement is used to prepare sintering paste Composition).

As the first connecting object component, preparation is coated with the power semiconductor of Ni/Au on joint face.As second Connecting object component, preparation are coated with the power semiconductor of Cu on joint face.

Above-mentioned sintering silver paste agent is coated on the second connecting object component, and makes it with a thickness of about 70 μm, forms sintering Use paste layer.Then, on sintering paste layer, the above-mentioned first connecting object component of lamination obtains laminated body.

Obtained laminated body is placed in the reflow ovens of nitrogen atmosphere, then with the heating rate of 10 DEG C/min and 250 DEG C Peak temperature, heat laminated body 60 minutes, thus to the above-mentioned particle containing metallic atom contained in sintering paste into Row sintering passes through sinter connection above-mentioned first to form the interconnecting piece of the particle containing sinter and containing metallic atom With the second connecting object component, connection structural bodies A2 is obtained.

Obtained connection structural bodies A2 " Technovit4000 " for being added to the manufacture of Kulzer company is made into its solidification, is made Make the embedded resin for checking connection structural bodies.It is cut using ion milling machine (" IM4000 " of the high-new Co., Ltd.'s manufacture of Hitachi) The section of particle containing metallic atom out, and cut through the immediate vicinity of the connection structural bodies in the detection embedded resin.

Then, using transmission electron microscope FE-TEM (" JEM-2010FEF " anufactured by Japan Electron Optics Laboratory(JEOL)), lead to Energy dispersion type X-ray analyzer (" EX-470 " that hole field makes the manufacture of Co., Ltd. of institute) is crossed, to the grain containing metallic atom The contact portion of son and sintered body carries out element mapping, observes the disperse state of metal component.

By mapping the disperse state of above-mentioned metal, calculate the above-mentioned particle containing metallic atom periphery and above-mentioned burning Contact ratio between knot body.

[judgment criteria of contact ratio]

000: contact ratio is more than 80% and is 100% or less.

00: contact ratio is more than 50% and is 80% or less.

Zero: contact ratio is more than 30% and is 50% or less.

△: contact ratio is 5% or more and 30% or less.

×: contact ratio is 5% or less.

(12) flatness of the power semiconductor in connection structural bodies A2

The flatness of the power semiconductor of connection structural bodies A2 obtained in evaluation for above-mentioned (11), uses height Precision laser displacement meter (" LK-G5000 " of the manufacture of Keyence Co., Ltd.) measurement maximum displacement and maximum displacement.Root According to obtained measured value, above-mentioned flatness is acquired by following equatioies.

Flatness (μm)=maximum displacement (μm)-least displacement (μm)

[judgment criteria of flatness]

000: flatness is 0.5 μm or less.

00: flatness is more than 0.5 μm and is 1 μm or less.

Zero: flatness is more than 1 μm and is 5 μm or less.

△: flatness is more than 5 μm and is 10 μm or less.

×: flatness is more than 10 μm.

(13) connection reliability of connection structural bodies A2

Connection structural bodies A2 obtained in the evaluation of above-mentioned (11) is packed into cold-hot impact tester (ESPEC Co., Ltd. " TSA-101S-W " of manufacture) in, will at -40 DEG C of minimum temperature the retention time be 30 minutes, protect at 200 DEG C of maximum temperature It holds the treatment conditions that the time is 30 minutes to recycle as one, and after 3000 circulations, with shear strength test instrument (" STR-1000 " of the manufacture of RHESCA Co., Ltd.) measurement adhesive strength.

[judgment criteria of connection reliability]

000: adhesive strength is more than 40MPa.

00: adhesive strength is more than 30MPa and is 40MPa or less.

Zero: adhesive strength is more than 20MPa and is 30MPa or less.

△: adhesive strength is more than 10MPa and is 20MPa or less.

×: adhesive strength is 10MPa or less.

Table 1 is indicated using connection structural bodies obtained by the particle containing metallic atom obtained in each embodiment and comparative example The Evaluation results of A1 and connection structural bodies A2.

Connection structural bodies A1 and connection structure obtained by using the particle containing metallic atom obtained in each embodiment In body A2, flatness and connection reliability are all very excellent, therefore can inhibit generation and the crack of warpage.Especially show, Connection structural bodies A2 obtained also has excellent performance under the conditions of non-pressurised.

Symbol description

A: connection structural bodies

10: the particle containing metallic atom

11: substrate particle

12: metal portion

12a: the first metal portion

12b: the second metal portion

13: protrusion

14: recess portion

20: sintered body

50: adhesive layer

Claims

1. a kind of connection structural bodies, with adhesive layer, the adhesive layer contains: the sintered body of metallic and containing metal Atomic particle, wherein

The particle containing metallic atom and the sintered body are contacted by chemical bond,

In the section of the adhesive layer, the outer perimeter of the particle containing metallic atom 5% or more with the sintered body Contact.

2. connection structural bodies according to claim 1, wherein the particle containing metallic atom have substrate particle and The metal portion being configured on the substrate particle surface.

3. connection structural bodies according to claim 2, wherein the metal portion has multiple protrusions in outer surface.

4. connection structural bodies according to claim 3, wherein the average diameter of the base portion of the protrusion be 3nm or more and 5000nm or less.

5. connection structural bodies according to claim 3 or 4, wherein the average height of the protrusion be 1nm or more and 1000nm or less.

6. the connection structural bodies according to any one of claim 3~5, wherein in the total of the outer surface of the metal portion In surface area 100%, the protrusion accounts for 30% or more.

7. the connection structural bodies according to any one of claim 2~6, wherein nickel, chromium, platinum in the metal portion and The total amount of rhodium is 30 mass % or less relative to the gross mass of the metal portion.

8. the connection structural bodies according to any one of claim 2~7, wherein the metal portion contain selected from it is following at One or more of point: gold, silver, tin, copper, germanium, indium, palladium, tellurium, thallium, bismuth, zinc, arsenic, selenium and containing in these metallic elements The alloy of at least one metallic element.

9. the connection structural bodies according to any one of claim 2~8, wherein formed on the surface of the substrate particle There are multiple recess portions.

10. a kind of particle containing metallic atom, is used for connection structural bodies according to any one of claims 1 to 9.

11. a kind of bonding composition contains the particle and metallic described in any one of claim 10 containing metallic atom.