CN109983544A - Electroconductive particle, conductive material and connection structural bodies - Google Patents

Electroconductive particle, conductive material and connection structural bodies Download PDF

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Publication number
CN109983544A
CN109983544A CN201880004430.7A CN201880004430A CN109983544A CN 109983544 A CN109983544 A CN 109983544A CN 201880004430 A CN201880004430 A CN 201880004430A CN 109983544 A CN109983544 A CN 109983544A
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CN
China
Prior art keywords
electrode
electroconductive particle
conductive material
semiconductor particles
solder
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CN201880004430.7A
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Chinese (zh)
Inventor
久保田敬士
西冈敬三
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Sekisui Chemical Co Ltd
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Sekisui Chemical Co Ltd
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Publication date
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Publication of CN109983544A publication Critical patent/CN109983544A/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/10—Bump connectors; Manufacturing methods related thereto
    • H01L2224/11—Manufacturing methods

Abstract

The present invention provides a kind of electroconductive particle, can easily install at low temperature, and can effectively improve the impact resistance of interconnecting piece.Electroconductive particle of the invention, has: fusing point is lower than 200 DEG C of semiconductor particles, and the covering portion being set on the surface of the semiconductor particles, wherein the covering portion contains silver.

Description

Electroconductive particle, conductive material and connection structural bodies
Technical field
The present invention relates to a kind of electroconductive particles containing solder.Moreover, it relates to which a kind of use the electric conductivity The conductive material and connection structural bodies of particle.
Background technique
The anisotropic conductive materials such as anisotropic conductive paste and anisotropic conductive film are well-known.It is described each In anisotropy conductive material, electroconductive particle is dispersed in resin binder.
The anisotropic conductive material is for obtaining various connection structural bodies.As based on the anisotropic conductive material Expect the connection carried out, such as the connection between flexible printing substrate and glass substrate (FOG (Film on Glass)), semiconductor The company between connection (COF (Chip on Glass)), semiconductor chip and glass substrate between chip and flexible printing substrate It connects between (COG (Chip on Glass)) and flexible printing substrate and epoxy glass substrate (FOB (Film on Board)) Connection etc..
By the anisotropic conductive material, for example, the electricity of electrode and glass epoxy substrate to flexible printing substrate When pole is electrically connected, the anisotropic conductive material containing electroconductive particle is configured on glass epoxy substrate.Then, right Flexible printing substrate carries out lamination, heating and pressurization.Solidify anisotropic conductive material as a result, passes through electroconductive particle It is electrically connected between electrode, obtains connection structural bodies.
The conductive material of the anisotropic conductive material etc. is as shown in following Patent Documents 1 to 3.
Following patent documents 1 disclose a kind of anisotropic conductive material, containing electroconductive particle and containing leading at this The resin component that will not be fully cured under the fusing point of conductive particles.As the electroconductive particle, specifically, can enumerate: tin (Sn), the metals such as indium (In), bismuth (Bi), copper (Cu), zinc (Zn), lead (Pb), cadmium (Cd), tin (Ga), silver-colored (Ag), thallium (Tl), with And the alloy of these metals.
It is disclosed the following contents in patent document 1.It by following steps, is electrically connected between electrode: described being higher than The fusing point of electroconductive particle, and the resin component will not be completed at cured temperature, to the tree of anisotropic conductive material The heating stepses that rouge is heated make the resin component of the resin component carry out cured curing schedule.In addition, patent document 1 describes and is installed under the temperature curve shown in Fig. 8 of patent document 1.In patent document 1, to anisotropy conduction material In the resin component that material is not fully cured at a temperature of being heated, electroconductive particle melting.
Following patent document 2 discloses a kind of adhesive tape (conductive material) comprising contains heat-curing resin Resin layer, solder powder and curing agent, wherein the solder powder and the curing agent are present in the resin layer.
Following patent document 3 discloses a kind of electroconductive particle, has particle and passes through nothing on the surface of the particle The conductive film covering that electrolytic plating method is formed.The conductive film covering, which has, passes through what electroless process was sequentially formed from inside Nickel plated film, tin plated film and bismuth plated film.In addition, the conductive film has silver coating in outmost surface.The electroconductive particle It can be used as anisotropic conductive material.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2004-260131 bulletin
Patent document 2:WO2008/023452A1
Patent document 3:WO 2006/085481A1
Summary of the invention
The technical problems to be solved by the invention
In current-conducting material, electroconductive particle or semiconductor particles are oxidized easily, and can't improve enough connection sometimes Interelectrode interconnecting piece impact resistance.In particular, the substrate etc. after being installed using conductive material, the impact resistance of interconnecting piece When not high enough, since whereabouts of substrate etc. is impacted, crack etc. may occur on interconnecting piece.As a result, it is difficult to sufficiently improve electrode it Between conducting reliability.
It as the method for the impact resistance for improving interconnecting piece, can enumerate: replace passing using SAC (tin-silver-copper alloy) particle The method of the electroconductive particle or semiconductor particles of system.However, the fusing point of SAC particle is 200 DEG C or more, and it is difficult at low temperature Installation.
The purpose of the present invention is to provide a kind of electroconductive particles, can easily install at low temperature, and can be with Effectively improve the impact resistance of interconnecting piece.In addition, it is another object of the present invention to provide use above-mentioned electroconductive particle Conductive material and connection structural bodies.
For solving the technical solution of technical problem
Extensive aspect according to the present invention, provides a kind of electroconductive particle, have: fusing point is lower than 200 DEG C of solder grain Son, and the covering portion being set on the surface of the semiconductor particles, wherein the covering portion contains silver.
The particular aspects of electroconductive particle according to the present invention, wherein the semiconductor particles contain tin and bismuth.
The particular aspects of electroconductive particle according to the present invention, wherein in 100 weight % electroconductive particles, the silver contains Amount is 1 weight % or more and 20 weight % or less.
The particular aspects of electroconductive particle according to the present invention, wherein in the surface area whole 100% of the semiconductor particles In, it by the surface area that is covered by the covering portion is 80% or more in the surface of the semiconductor particles.
The particular aspects of electroconductive particle according to the present invention, wherein the covering portion with a thickness of 0.1 μm or more and 5 μ M or less.
The particular aspects of electroconductive particle according to the present invention, wherein the outer surface of the semiconductor particles and the cladding Has nickeliferous metal portion between portion.
Extensive aspect according to the present invention, provides a kind of conductive material, contains the electroconductive particle and thermosetting The property changed compound.
The particular aspects of electroconductive particle according to the present invention, wherein in 100 weight % of conductive material, the electric conductivity The content of particle is more than 50 weight %.
The particular aspects of electroconductive particle according to the present invention, wherein the Thermocurable compound contains with polyethers The Thermocurable compound of skeleton.
The particular aspects of electroconductive particle according to the present invention, it is 50 DEG C or more and 140 that the conductive material, which contains fusing point, DEG C fluxing agent below.
The particular aspects of electroconductive particle according to the present invention, viscosity at 25 DEG C be 20Pas or more and 600Pas or less.
The particular aspects of electroconductive particle according to the present invention, the conductive material are conductive paste.
Extensive aspect according to the present invention, provides a kind of connection structural bodies, have: surface has at least one first electricity First connecting object component of pole, surface have the second connecting object component of at least one second electrode, and by described the The interconnecting piece that one connecting object component and second connection link together to component, wherein the material of the interconnecting piece contains There is an electroconductive particle, the first electrode and the second electrode realize electricity by the solder portion in the interconnecting piece Connection.
The particular aspects of connection structural bodies according to the present invention, wherein along the first electrode, the interconnecting piece and institute The stack direction for stating second electrode, when observing the first electrode and the opposed part of the second electrode, the first electrode 50% or more with the second electrode in the area 100% of opposed part is configured with the solder portion in the interconnecting piece.
The effect of invention
Electroconductive particle of the invention includes semiconductor particles of the fusing point lower than 200 DEG C and is set to the semiconductor particles surface On covering portion.In electroconductive particle of the invention, the covering portion contains silver.On having due to electroconductive particle of the invention Technical characteristic is stated, therefore, can easily be installed at low temperature, and the impact resistance of interconnecting piece can be effectively improved.
Detailed description of the invention
Fig. 1 is connection structural bodies obtained from the conductive material schematically shown using an embodiment of the invention Sectional view.
Fig. 2 (a)~(c) is the conductive material that explanation uses one embodiment of the present invention, manufactures the side of connection structural bodies The sectional view of each step of one example of method.
Fig. 3 is the sectional view for indicating the variation of connection structural bodies.
Fig. 4 is the sectional view for indicating the electroconductive particle of first embodiment of the invention.
Fig. 5 is the sectional view for indicating the electroconductive particle of second embodiment of the present invention.
Symbol description
1,1X ... connection structural bodies
2 ... first connecting object components
2a ... first electrode
3... the second connecting object component
3a ... second electrode
4,4X ... interconnecting pieces
4A, 4XA ... solder portion
4A, 4XB ... solidfied material portion
11 ... conductive materials
11A ... electroconductive particle
11B ... Thermocurable ingredient
21,31 ... electroconductive particles
22 ... semiconductor particles
23 ... covering portion
32 ... metal portions
Specific embodiment
Hereinafter, detailed description of embodiments of the present invention.
(electroconductive particle)
The covering portion that electroconductive particle of the invention has semiconductor particles and is configured on the surface of the semiconductor particles. In electroconductive particle of the invention, the fusing point of the solder portion is lower than 200 DEG C.In electroconductive particle of the invention, the cladding Contain silver in portion.
The present invention can be installed at a lower temperature due to having the technical characteristic, and can be effective The impact resistance of ground raising interconnecting piece.
In addition, the conductive material containing electroconductive particle is set sometimes through silk-screen printing etc. when preparation connection structural bodies It is placed on the connecting objects component such as substrate, then, places a period of time until being electrically connected between electrode.With regard to existing electroconductive particle Speech, for example, placing a period of time, during which metal ion may be dissolved out from electroconductive particle.The metal ion of dissolution accelerates sometimes The solidification of Thermocurable compound etc. in conductive material, increases the viscosity of conductive material.As a result, cannot be by the weldering of electroconductive particle Material is effectively arranged on electrode, and interelectrode conducting reliability reduces sometimes.The present invention is due to using above-mentioned technical characteristic, i.e., Make to place a period of time after the conductive material containing electroconductive particle is arranged, is also possible to prevent the thickening of conductive material, it can The solder of electroconductive particle to be effectively arranged on electrode, and it can sufficiently improve the conducting reliability between electrode.
In addition, in the present invention, for the narrow electrode of width between counter electrode width and electrode, even if the grain of semiconductor particles Diameter becomes smaller, and is also possible to prevent semiconductor particles surface oxidation, can keep the wetability of solder well.In current-conducting material, When width is narrow between electrode width or electrode, there is the tendency that solder on the electrode is difficult to assemble.In the present invention, even if electrode width Or width is narrow between electrode, the solder of electroconductive particle can also be fully gathered on electrode.
Heretofore described electroconductive particle includes that the covering portion of argentiferous will be largely responsible for realizing said effect.
In addition, in the present invention, due to having above-mentioned technical characteristic, when being electrically connected between electrode, multiple electric conductivity grains Between son is easy to be gathered in comparative electrode up and down, multiple electroconductive particles can be effectively arranged on electrode (line).In addition, more A part of a electroconductive particle, which is difficult to be set to, not yet to be formed in the region (space) of electrode, and can substantially reduce setting The amount of electroconductive particle in the region for not yet forming electrode.It is thus possible to improve the conducting reliability between electrode.Separately Outside, the electrical connection between the laterally adjacent electrode that should not be connected can be prevented, insulating reliability can be improved.
Also, the present invention can prevent interelectrode position deviation.In the present invention, by the conduction material containing electroconductive particle When the first connecting object component that material is configured at upper surface is overlapped with the second connecting object component, even if in first electrode and second Electrode is aligned there are in the state of deviation, can connect first electrode and second electrode (self alignment effect) with correcting action.
Fig. 4 is the cross-sectional view for showing the electroconductive particle of first embodiment of the invention.
Electroconductive particle 21 shown in Fig. 4 includes semiconductor particles 22 and the covering portion being set on the surface of semiconductor particles 22 23.The fusing point of semiconductor particles 22 is lower than 200 DEG C.Covering portion 23 contains silver.Covering portion 23 wraps the surface of semiconductor particles 22 It covers.Electroconductive particle 21 is that the surface of semiconductor particles 22 is wrapped by coating particles obtained from portion 23 coats.The covering portion, can It, can also be with the surface of semiconductor particles described in endless all standing the surface of the semiconductor particles is completely covered.The semiconductor particles It can have the part not yet covered by the covering portion.
Fig. 5 shows the cross-sectional view of the electroconductive particle of second embodiment of the invention.
Electroconductive particle 31 shown in Fig. 5 includes semiconductor particles 22, the metal being set on the surface of semiconductor particles 22 Portion 32 and the covering portion 23 being set on the surface of metal portion 32.Electroconductive particle 31 is in semiconductor particles 22 and covering portion 23 Between have metal portion 32.Metal portion 32 coats the surface of semiconductor particles 22.Surface of the covering portion 23 to metal portion 32 It is coated.Covering portion 23 contains silver.Metal portion 32 contains nickel.Electroconductive particle 31 is the surface of semiconductor particles 22 by metal portion 32 and covering portion 23 coat obtained from coating particles.
The partial size of the electroconductive particle is preferably 0.5 μm or more, and more preferable 1 μm or more, further preferred 3 μm or more, Particularly preferred 5 μm or more, preferably 100 μm hereinafter, more preferable 40 μm hereinafter, further preferably 30 μm hereinafter, and preferably 20 μm hereinafter, particularly preferably 15 μm hereinafter, most preferably 10 μm or less.The partial size of the electroconductive particle the lower limit with When below the upper and described upper limit, the solder in electroconductive particle can be further effectively arranged on electrode.The conduction The partial size of property particle is particularly preferably 5 μm or more and 30 μm or less.
The average grain diameter of the electroconductive particle indicates number average bead diameter.The average grain diameter of electroconductive particle, for example, can lead to It crosses and uses electron microscope or arbitrary 50 electroconductive particles of optical microphotograph sem observation, and calculate being averaged for each electroconductive particle Value, or acquired by the survey of laser diffraction type size distribution.
The coefficient of variation (CV value) of the partial size of the electroconductive particle is preferably 5% or more, and more preferably 10% or more, it is excellent 40% is selected as hereinafter, more preferably 30% or less.The coefficient of variation of the partial size of the electroconductive particle more than the lower limit and When below the upper limit, the solder of electroconductive particle can be further effectively arranged on electrode.But the electric conductivity The CV value of the partial size of particle, can be below 5%.
The coefficient of variation (CV value) can measure in the following manner.
CV value (%)=(ρ/Dn) × 100
P: the standard deviation of the partial size of electroconductive particle
Dn: the average value of the partial size of electroconductive particle
The shape of the electroconductive particle is not particularly limited.The shape of the electroconductive particle, can be it is spherical, can also Be planar as etc. it is spherical other than shape.
Hereinafter, other details that will illustrate electroconductive particle.
(semiconductor particles)
The semiconductor particles, central part and outer surface any one be all to be formed by solder.During the semiconductor particles are Center portion point and outer surface are the particle of solder.The substrate particle that is formed by the material except solder and has and be set to the base The electroconductive particle of solder portion on the surface of material particle, in the case where replacing the semiconductor particles using the particle, electric conductivity Particle is difficult to concentrate on electrode.In addition, existing and being moved on electrode since the solder adhesiveness between electroconductive particle is low Electroconductive particle is easy to be moved to the tendency outside electrode, and there is also the tendencies that the inhibitory effect of interelectrode position deviation reduces.
The solder is preferably that fusing point is 450 DEG C of metals (low-melting-point metal) below.The semiconductor particles are preferably molten Point is 450 DEG C of metallics (low-melting-point metal particle) below.The low-melting-point metal particle is containing low-melting-point metal Particle.The low-melting-point metal is that fusing point is 450 DEG C of metals below.The fusing point of low-melting-point metal is preferably 300 DEG C hereinafter, more excellent Choosing is lower than 200 DEG C, further preferably 160 DEG C or less.
In electroconductive particle of the invention, the fusing point of the semiconductor particles is lower than 200 DEG C.From being further easy in low temperature From the perspective of lower installation, the semiconductor particles are preferably the eutectic solder that fusing point is lower than 200 DEG C, and more preferable fusing point is lower than 150 DEG C of eutectic solder.
From the viewpoint of further being easy to install at low temperature, the preferably described semiconductor particles contain tin and bismuth.It is described In the 100 weight % of metal contained in semiconductor particles, Theil indices are preferably 30 weight % or more, more preferably 40 weight % with On, further preferably 70 weight % or more, particularly preferably 90 weight % or more.The content of tin is in institute in the semiconductor particles When stating lower limit or more, the connection reliability between solder portion and electrode is further improved.The gold contained in the semiconductor particles Belong in 100 weight %, bi content is preferably 40 weight % or more, more preferably 45 weight % or more, further preferably 48 weights Measure % or more, particularly preferably 50 weight % or more.When bi content in the semiconductor particles is more than the lower limit, solder portion Connection reliability between electrode further improves.
The content of the tin and bismuth can be by using high-frequency inductive coupling plasma body emission spectrometer (Co., Ltd.'s hole Field production manufactured " ICP-AES ") or the fluorescent X-ray analysis instrument (" EDX- of Shimadzu Scisakusho Ltd's manufacture 800HS ") measurement.
By using the semiconductor particles, melt solder is simultaneously joined to electrode, and solder portion makes to be connected between electrode.For example, weldering Material portion and electrode are easy face contact and not point contact, therefore connect resistance reduction.In addition, by using the semiconductor particles, Solder portion and the adhesive strength of electrode improve, as a result, the removing of solder portion and electrode is more difficult to occur, and reliability and connection is connected Reliability further improves.
The low-melting-point metal of the semiconductor particles is constituted, fusing point is lower than 200 DEG C, and there is no particular restriction.The low melting point Metal is preferably the alloy containing tin or tin.As the alloy, can enumerate tin-silver alloy, tin-copper alloy, tin-silver-copper alloy, Tin-bismuth alloy electroplating, tin-zinc alloy, Sn-In alloy etc..From the viewpoint of there is excellent wetability to electrode, the low melting point Metal is preferably tin, tin-silver alloy, tin-silver-copper alloy, tin-bismuth alloy electroplating, Sn-In alloy.More preferably tin-bismuth alloy electroplating, tin- Indium alloy.
Above-mentioned semiconductor particles, are based on the fusible term of JIS Z 3001, and preferred liquid phase line is 450 DEG C of packing materials below. It as the ingredient of the semiconductor particles, can enumerate: the metal component of zinc, gold, silver, lead, copper, tin, bismuth, indium etc..Preferably fusing point is low And unleaded tin indium class (117 DEG C of eutectics) or tin bismuth class (139 DEG C of eutectics).That is, the semiconductor particles are preferably free of lead, it is excellent Choosing is containing tin and indium or contains tin and bismuth.
From the viewpoint of the bond strength for further improving solder portion and electrode, the semiconductor particles can contain The metals such as nickel, copper, antimony, aluminium, zinc, iron, gold, titanium, phosphorus, germanium, tellurium, cobalt, bismuth, manganese, molybdenum, palladium.In addition, improving solder from further From the perspective of adhesive strength between portion and electrode, the preferably described semiconductor particles contain nickel, copper, antimony, aluminium or zinc.Just more into one From the perspective of step improves the adhesive strength between solder portion and electrode, these are used to improve the content of the metal of adhesive strength, In 100 weight % of semiconductor particles, preferably 0.0001 weight % or more, preferably 1 weight % or less.
The partial size of the semiconductor particles is preferably 0.5 μm or more, more preferably 1 μm or more, further preferably 3 μm with On, particularly preferably 5 μm or more, preferably 100 μm hereinafter, more preferably 40 μm hereinafter, further preferably 30 μm hereinafter, simultaneously And preferably 20 μm hereinafter, particularly preferably 15 μm hereinafter, most preferably 10 μm or less.The partial size of the semiconductor particles is above-mentioned When more than lower limit and below the above-mentioned upper limit, the solder in electroconductive particle can be further effectively arranged on electrode. The partial size of the semiconductor particles is particularly preferably 5 μm or more and 30 μm or less.
The partial size of the semiconductor particles indicates number average bead diameter.The partial size of semiconductor particles, can by with electron microscope or Arbitrary 50 semiconductor particles of optical microphotograph sem observation, calculate the average value of the partial size of each semiconductor particles, or spread out by laser Emitting particle size distribution measurement and acquire.
The coefficient of variation (CV value) of the partial size of the semiconductor particles is preferably 5% or more, and more preferably 10% or more, preferably For 40% hereinafter, more preferably 30% or less.The coefficient of variation of the partial size of the semiconductor particles is more than the lower limit and in institute When stating the upper limit or less, the solder in electroconductive particle can be further effectively arranged on electrode.But the solder grain The CV value of the partial size of son is smaller than 5%.
The coefficient of variation (CV value) can measure in the following manner.
CV value (%)=(ρ/Dn) × 100
P: the standard deviation of the partial size of semiconductor particles
Dn: the average value of the partial size of semiconductor particles
The shape of the semiconductor particles is not particularly limited.The shape of the semiconductor particles, can be spherical, be also possible to It is flat etc. it is spherical other than shape.
(covering portion)
The covering portion is set on the surface of the semiconductor particles.The covering portion contains silver.The covering portion can be with Only comprising silver, the metal except desilver also may include.Metal except the desilver for including in the covering portion does not limit especially System, can enumerate gold, copper, nickel, palladium and titanium etc..
In 100 weight % of electroconductive particle, the content of the silver is preferably 1 weight % or more, more preferably 5 weight % with On, further preferably 10 weight % or more, particularly preferably 11 weight % or more, preferably 20 weight % are hereinafter, more preferably 15 weight % are hereinafter, further preferred 13 weight % or less.The content of the silver more than above-mentioned lower limit and the above-mentioned upper limit with When lower, further it is easy to install at low temperature, can effectively further improves the impact resistance of interconnecting piece.
Interconnecting piece is effectively improved from the viewpoint of further easily installing at low temperature, and from further Impact resistance from the perspective of, in the surface area of the semiconductor particles whole 100%, the surface of the semiconductor particles is described The surface area (clad ratio) of covering portion covering, preferably 80% or more, more preferably 90% or more, the upper limit of the clad ratio is simultaneously It is not particularly limited.The clad ratio can be 100% or less.
The clad ratio can analyze the electroconductive particle by SEM-EDX, carry out Ag mapping (Ag Mapping it) is calculated with image analysis.
Interconnecting piece is effectively improved from the viewpoint of further easily installing at low temperature, and from further Impact resistance from the perspective of, the thickness of the covering portion is preferably 0.1 μm or more, more preferably 1 μm or more, preferably 5 μ M is hereinafter, more preferably 2 μm or less.It should be noted that the thickness of the covering portion is only to have to be set to the semiconductor particles The thickness of the covering portion of the part of covering portion on surface.When calculating the thickness of covering portion, do not consider not in the solder grain The part of covering portion is set on the surface of son.
In the case that the covering portion is only formed by silver, the thickness of the covering portion is preferably 0.1 μm or more, more preferably 0.5 μm or more, further preferably 1 μm or more, particularly preferably 1.5 μm or more.Preferably 5 μm hereinafter, more preferably 2 μm with Under.In the case that the covering portion is only formed by silver, the thickness of the covering portion is more than above-mentioned lower limit and below the above-mentioned upper limit When, it can further easily install at low temperature, can further effectively improve the impact resistance of interconnecting piece.
In addition, the covering portion can be single layer, it is also possible to two layers or more (multilayer).The covering portion is two layers or more In the case where (multilayer), the thickness of the covering portion refers to the thickness of the covering portion entirety.
The thickness of the covering portion can pass through the difference of the partial size of the partial size and electroconductive particle of the semiconductor particles To calculate.
Interconnecting piece is effectively improved from the viewpoint of further easily installing at low temperature, and from further Impact resistance from the perspective of, (thickness/the weldering of covering portion of the ratio between partial size of the thickness of the covering portion and the semiconductor particles Expect the partial size of particle) it is preferably 0.001 or more, more preferable 0.01 hereinafter, it is preferred that 5 hereinafter, more preferably 1 or less.
When electroconductive particle with the covering portion is used for conductive material, metallic can be effectively prevented from leading Conductive particles dissolution, can be effectively prevented the thickening of conductive material.In addition, electroconductive particle has the covering portion, thus It can be effectively prevented the oxidation of the solder surface of electroconductive particle, can further keep the wettability of solder well.
Also, before conductive connection (installation), the solder of the semiconductor particles preferably in electroconductive particle and described The silver that covering portion includes independently exists, and without alloying.In such a case it is possible to make the conduction before being conductively connected Property particle melts at the fusing point of the semiconductor particles.The semiconductor particles preferably fusing point is lower than 200 DEG C of eutectic solder, because This, the electroconductive particle before being conductively connected (installation) can melt at relatively low temperatures, and be easy to carry out at low temperature It is conductively connected (installation).In addition, the heat after conductive connection (installation), preferably by applying at conductive connection (installation) Amount, the silver for making the solder of the semiconductor particles of electroconductive particle include with the covering portion carry out alloying.In this case, The fusing point for being conductively connected the interconnecting piece (weld part) after (installation) is higher than the fusing point of the semiconductor particles, therefore can be effectively Improve the impact resistance of interconnecting piece (weld part).
(metal portion)
The electroconductive particle has preferably between the outer surface of the semiconductor particles and the covering portion contains nickel Metal portion.The electroconductive particle is preferably provided with the metal portion being set on the surface of the semiconductor particles, and is set to institute State the covering portion on metal portion.The electroconductive particle can further easily by meeting the preferred embodiment It installs at low temperature, can further effectively improve the impact resistance of interconnecting piece.
The metal portion preferably comprises nickel.The metal portion can also contain the metal other than nickel.The metal portion contains Nickel other than metal be not particularly limited, gold, silver, copper, palladium and titanium etc. can be enumerated.
Interconnecting piece is effectively improved from the viewpoint of further easily installing at low temperature, and from further Impact resistance from the perspective of, the thickness of the metal portion is preferably 0.1 μm or more, more preferably 1 μm or more, preferably 5 μ M is hereinafter, more preferably 2 μm or less.It should be noted that the thickness of the metal portion, simply means to: having in the semiconductor particles The metal portion thickness of the part of the metal portion configured on surface.When calculating the thickness of metal portion, do not consider in the solder grain The part of metal portion is not configured on the surface of son.
When the metal portion is only formed by nickel, from the viewpoint of further being easy to install at low temperature, and from more From the perspective of the impact resistance for effectively further improving interconnecting piece, the thickness of the metal portion is preferably 0.1 μm or more, more Preferably 0.5 μm or more, further preferably 1 μm or more, preferably 5 μm are hereinafter, more preferably 2 μm or less.
In addition, the metal portion can be single layer, it is also possible to two layers or more (multilayer).The metal portion is two layers or more In the case where (multilayer), the thickness of the metal portion refers to the thickness of the metal portion entirety.
For example, by using the cross section of transmission electron microscope (TEM) observation electroconductive particle, the available gold The thickness in category portion.
From the viewpoint of further easily installing at low temperature, and further effectively improve interconnecting piece From the perspective of impact resistance, the ratio between partial size of the thickness of the metal portion and the semiconductor particles (thickness/solder of metal portion The partial size of particle) it is preferably 0.001 or more, more preferably 0.01 or more, preferably 5 hereinafter, more preferably 1 or less.
(conductive material)
Conductive material of the invention preferably comprises above-mentioned electroconductive particle and Thermocurable compound.
From the viewpoint of further effectively being set on electrode the solder of electroconductive particle, the conductive material It is preferred that being liquid, preferably conductive paste at 25 DEG C.
From the viewpoint of further effectively being set on electrode the solder in electroconductive particle, the conduction material Expect that viscosity (η 25) at 25 DEG C is preferably 20Pas or more, more preferably 30Pas or more, preferably 600Pas with Under, more preferably 300Pas or less.The viscosity (η 25) can be according to the type and combined amount appropriate adjustment of blending constituent.
E type viscosimeter (" TVE22L " of the manufacture of Industry Co., Ltd, Toshiba) etc. can be used for example in the viscosity (η 25) It is measured under conditions of 25 DEG C, 5rpm.
From the viewpoint of further effectively being set on electrode the solder in electroconductive particle, the electric conductivity Viscosity (η mp) of the particle under fusing point is preferably 0.1Pas or more, more preferably 0.5Pas or more, preferably 5Pas with Under, more preferably 1Pas or less.The viscosity (η mp) can be according to the type and use level appropriate adjustment of blending constituent.
The fusing point of electroconductive particle is easy to the temperature having an impact on the solder migration to electrode of electroconductive particle.
The viscosity (η mp) of the conductive material of the fusing point of the electroconductive particle can be used
STRESSTECH (manufacture of REOLOGICA company) etc., with the strain controlling of 1rad, the frequency of 1Hz, 20 DEG C/minute The condition of the fusing point of heating rate and 40 DEG C~electroconductive particle measures.In the measurement, by the fusing point of electroconductive particle Viscosity (η mp) of the viscosity at place as conductive material.
The conductive material can be used as the use such as conductive paste and conductive film.The conductive paste be preferably it is each to Anisotropic conductive paste, the conductive film are preferably anisotropic conductive film.From further effectively will be in electroconductive particle From the perspective of solder is set on electrode, the conductive material is preferably conductive paste.The conductive material is suitable for electricity The electrical connection of pole.The conductive material is preferably circuit connection material.
From the viewpoint of further effectively being set on electrode the solder in electroconductive particle, the conduction material Expect in 100 weight %, the content of the electroconductive particle is preferably greater than 50 weight %.In 100 weight % of the conductive material In, in the case that the content of the electroconductive particle is greater than 50 weight %, further play improve installation under low temperature and The impact resistance of interconnecting piece.In the 100 weight % of conductive material, the content of the electroconductive particle be preferably 50 weight % with On, more preferably 70 weight % or more, preferably 90 weight % are hereinafter, more preferably 80 weight % or less.The electric conductivity grain When the content of son is more than the lower limit and below the upper limit, the solder of electroconductive particle further can effectively be set It is placed on electrode, is easy that a large amount of electroconductive particles are arranged between electrode.From the sight for further effectively improving conducting reliability Point sets out, and the content of the preferably described electroconductive particle is more.
Hereinafter, by being illustrated to each ingredient that conductive material contains, it should be noted that in the following description, " (methyl) acrylic acid " refers to one or both of " acrylic acid " and " methacrylic acid ", and " (methyl) acrylate " refers to One or both of " acrylate " and " methacrylate ".
(Thermocurable compound)
The conductive material preferably comprises Thermocurable compound.The Thermocurable compound can be sent out by heating Raw cured compound.As the Thermocurable compound, oxetane compound, epoxide, epithio can be enumerated Compound, (methyl) acrylic compounds, phenolic compounds, amino-compound, unsaturated polyester compound, polyurethane chemical combination Object, polysiloxane compound and polyimide compound etc..It is further good from the curability and viscosity for making conductive material, and From the perspective of improving connection reliability into a more step, the preferably described Thermocurable compound is epoxide or epithio chemical combination Object.The Thermocurable compound may be used alone, can also be used in combination two or more.
From the viewpoint of further effectively being set on electrode the solder of electroconductive particle, the Thermocurable Compound preferably comprises the Thermocurable compound with polyether skeleton.
As the Thermocurable compound with polyether skeleton, can enumerate: carbon atom is 3~12 and in alkyl chain Two ends have the compound of glycidyl ether；And with carbon atom be 2-4 polyether skeleton, and have the polyethers bone The polyether-type epoxide etc. of structural unit made of 2~10, frame continuous bondings.
It is led from the viewpoint of the heat resistance of solidfied material for further improving conductive material, and from further reduction From the perspective of the dielectric constant of the solidfied material of electric material, the Thermocurable compound preferably comprises the heat with triazine skeleton Curability compound.
As the Thermocurable compound with triazine skeleton, triazine triglycidyl ether etc., daily outputization can be enumerated Learn Industrial Co., Ltd TEPIC series (TEPIC-G, TEPIC-S, TEPIC-SS, TEPIC-HP, TEPIC-L, TEPIC-PAS, TEPIC-VL, TEPIC-UC) etc..
As the epoxide, aromatic epoxide can be enumerated.The epoxide is preferably resorcinol The crystal epoxidations such as type ring oxygen compound, naphthalene type ring oxygen compound, biphenyl type epoxy compound, diphenyl ketone type epoxide Close object.The epoxide is preferably solid under room temperature (23 DEG C) and melting temperature is solder melt point epoxidation below Close object.The melting temperature be preferably 100 DEG C hereinafter, more preferably 80 DEG C hereinafter, and preferably 40 DEG C or more.By using Above-mentioned preferred epoxide, in the stage for being fitted with connecting object component, viscosity is high, is assigned and being accelerated by impacts such as carryings When spending, the position deviation of the first connecting object component and the second connecting object component can be inhibited.Also, by using above-mentioned excellent The viscosity of conductive material can be greatly reduced, and can make conduction by heat when being solidified in the epoxide of choosing The cohesion of solder is effectively performed in property particle.
From the viewpoint of further effectively being set on electrode the solder in electroconductive particle, the heat cure Property compound preferably be contained at 25 DEG C be liquid Thermocurable compound.As it is described at 25 DEG C be liquid heat cure Property compound, can enumerate epoxide and episulfide compounds etc..
In the 100 weight % of conductive material, the content of the Thermocurable compound is preferably 20 weight % or more, more Preferably 40 weight % or more, further preferably 50 weight % or more, and preferably 99 weight % are hereinafter, more preferably 98 Weight % hereinafter, further preferably 90 weight % hereinafter, particularly preferably 80 weight % or less.The Thermocurable compound Content more than the lower limit and below the upper limit when, the solder of electroconductive particle further can effectively be set It is placed on electrode, further inhibits interelectrode position deviation, further improve interelectrode conducting reliability.From more into From the perspective of one step improves impact resistance, the content of the preferably described Thermocurable compound is more.
(thermal curing agents)
The conductive material preferably comprises thermoinitiators.The conductive material preferably comprise the Thermocurable compound and Thermal curing agents.The Thermocurable agent just looks like heat cure to the Thermocurable compound.It, can as the Thermocurable agent Enumerate: imidazole curing agent, phenol curing agent, polythiol hardener, amine hardener, anhydride curing agent, hot cation curing agent and heat are certainly By base producing agent etc..The thermal curing agents, can be used alone, and can also be applied in combination two or more.
From the viewpoint of it further solidify conductive material can rapidly at low temperature, the Thermocurable agent is excellent It is selected as imidazole curing agent, polythiol hardener or amine hardener.In addition, from the Thermocurable compound and the heat cure is improved From the perspective of the storage stability of agent, the thermal curing agents are preferably latent curing agent.Latent curing agent is preferably latent Volt property imidazole curing agent, latency polythiol hardener or latency amine hardener.It should be noted that the Thermocurable agent can To be coated by polymer substances such as polyurethane resin or polyester resin.
The imidazole curing agent is not particularly limited.It as the imidazole curing agent, can enumerate: 2-methylimidazole, 2- second Base -4-methylimidazole, 1- cyano ethyl -2- phenylimidazole, 1- cyano ethyl -2- phenylimidazole trimellitic acid, 2,4- diamino - 6- [2'- methylimidazolyl-is (1')]-ethyl-s-triazine, 2,4- diamino -6- [2'- methylimidazolyl-is (1')]-ethyl-s- Triazine isocyanuric acid adduct etc..
The polythiol hardener is not particularly limited.As the polythiol hardener, can enumerate: trimethylolpropane tris- Six -3-thiopropionate of 3-thiopropionate, four -3-thiopropionate of pentaerythrite and dipentaerythritol etc..
The amine hardener is not particularly limited.It as the amine hardener, can enumerate: hexamethylene diamine, eight methylenes Base diamines, decamethylene diamine, 3,9- bis- (3- aminopropyls) -2,4,8,10- tetrahydro spiral shell [5.5] hendecane, bis- (4- amino rings Hexyl) methane, m-phenylene diamine (MPD) and diaminodiphenylsulfone etc..
The hot cation curing agent is not particularly limited.As the hot cation curing agent, iodine-type sun can be enumerated Cationic cure agent, oxygen type cation curing agent and sulphonium type cation curing agent etc..As the iodine-type cation curing agent, Bis- (4- tert-butyl-phenyl) iodine hexafluorophosphates etc. can be enumerated.As the oxygen type cation curing agent, front three can be enumerated Base oxygen tetrafluoroborate etc..As the sulphonium type cation curing agent, three-p-methylphenyl sulfonium hexafluorophosphates etc. can be enumerated.
The hot radical producing agent is not particularly limited.As the hot radical producing agent, azo compounds can be enumerated Object and organic peroxide etc..As the azo-compound, azodiisobutyronitrile (AIBN) etc. can be enumerated.As described organic Peroxide, di-tert-butyl peroxide can be enumerated and cross methyl ethyl ketone peroxide etc..
The reacting initial temperature of the thermal curing agents is preferably 50 DEG C or more, and more preferably 70 DEG C or more, further preferably Be 80 DEG C or more, preferably 250 DEG C hereinafter, more preferably 200 DEG C hereinafter, further preferably 150 DEG C hereinafter, particularly preferably 140 DEG C or less.When the reacting initial temperature of the Thermocurable agent is more than the lower limit and more than the upper limit, electric conductivity grain The solder of son is further effectively arranged on electrode.The reacting initial temperature of the thermal curing agents be particularly preferably 80 DEG C with It is upper and 140 DEG C or less.
From the viewpoint of further effectively being set on electrode the solder of electroconductive particle, the Thermocurable The reacting initial temperature of agent is preferably higher than the fusing point of the solder of the electroconductive particle, more preferably high 5 DEG C or more, further excellent Select high 10 DEG C or more.
The reacting initial temperature of the Thermocurable agent refers to temperature when exothermic peak is begun to ramp up in DSC.
The content of the Thermocurable agent is not particularly limited.Relative to 100 parts by weight of Thermocurable compound, institute The content for stating Thermocurable agent is preferably 0.01 parts by weight or more, and it is more than more preferably 1 parts by weight, and preferably 200 weight Part hereinafter, more preferably 100 parts by weight hereinafter, below further preferred 75 parts by weight.The content of Thermocurable agent is under above-mentioned When limiting above, it is easy to solidify Thermocurable compound sufficiently.When the content of Thermocurable agent is below the upper limit, after solidification It is not easy residual and is not involved in cured excessive Thermocurable agent, and the heat resistance of solidfied material further improves.
(fluxing agent)
The conductive material preferably comprises fluxing agent.It, can be further effectively by electric conductivity by using fluxing agent The fluxing agent of particle is set on electrode.The fluxing agent is not particularly limited.As the fluxing agent, usual use can be used In the fluxing agent of engagement etc..
It as the fluxing agent, can enumerate: zinc chloride, the mixture of zinc chloride and inorganic halides, zinc chloride and inorganic Mixture, fuse salt, phosphoric acid, phosphoric acid derivatives, organohalogen compounds, hydrazine, amine compounds, organic acid and the rosin etc. of acid.It is described Fluxing agent can be used alone, or can be applied in combination two or more.
As the fuse salt, ammonium chloride etc. can be enumerated.It as the organic acid, can enumerate: lactic acid, citric acid, tristearin Acid, glutamic acid and glutaric acid etc..As above-mentioned rosin, activation rosin and disactivation rosin etc. can be enumerated.The fluxing agent is preferred For organic acid or rosin with more than two carboxyls.The fluxing agent can be the organic acid with more than two carboxyls, It can be pine resin.By using organic acid, the rosin with more than two carboxyls, interelectrode conducting reliability is further It improves.
As the organic acid with more than two carboxyls, can enumerate, such as: succinic acid, glutaric acid, adipic acid, pimelic acid, Suberic acid, azelaic acid, decanedioic acid etc..
As the amine compounds, can enumerate, such as: cyclohexylamine, dicyclohexyl amine, benzylamine, benzhydryl amine, imidazoles, benzene And imidazoles, phenylimidazole, carboxy benzimidazole, benzotriazole carboxyl benzotriazole etc..
Above-mentioned rosin is to make rosin as main component containing rosin acid.As the rosin, rosin acid, third can be enumerated Olefin(e) acid modified rosin etc..Fluxing agent is preferably rosin, more preferably rosin acid.By using the preferred fluxing agent, electrode Between conducting reliability further improve.
The fusing point (activation temperature) of the fluxing agent is preferably 10 DEG C or more, more preferably 50 DEG C or more, more preferably 70 DEG C or more, further preferably 80 DEG C or more, preferably 200 DEG C hereinafter, more preferably 190 DEG C hereinafter, further preferred 160 DEG C Hereinafter, still more preferably 150 DEG C hereinafter, and preferably 140 DEG C or less.The fusing point of the fluxing agent more than above-mentioned lower limit and When below the above-mentioned upper limit, fluxing agent effect is further effectively played, and the fluxing agent of electroconductive particle is further It is effectively arranged on electrode.The fusing point (activation temperature) of the fluxing agent is preferably 80 DEG C or more and 190 DEG C or less.It is described to help The fusing point (activation temperature) of flux is particularly preferably 80 DEG C or more and 140 DEG C or less.
Fusing point (activation temperature) as fluxing agent is 80 DEG C or more the and 190 DEG C fluxing agents below, can be enumerated: amber Amber acid (186 DEG C of fusing point), glutaric acid (96 DEG C of fusing point), adipic acid (152 DEG C of fusing point), pimelic acid (104 DEG C of fusing point) and suberic acid Dicarboxylic acids such as (142 DEG C of fusing points), benzoic acid (122 DEG C of fusing point), malic acid (130 DEG C of fusing point) etc..
In addition, the boiling point of the fluxing agent is preferably 200 DEG C or less.
It is preferably described fluxing from the viewpoint of being further effectively arranged on the solder of electroconductive particle on electrode The fusing point of agent is higher than the fusing point of the solder of the electroconductive particle, more preferably high 5 DEG C or more, further preferably high 10 DEG C or more.
For the viewpoint that the solder of electroconductive particle is effectively further set on electrode, the preferably described fluxing agent Fusing point it is higher than the reaction start temperature of the thermal curing agents, more preferably high 5 DEG C or more, further preferably high 10 DEG C or more.
The fluxing agent can be scattered in conductive material, can also be attached on the surface of electroconductive particle.
Since the fusing point of fluxing agent is higher than the fusing point of the solder of electroconductive particle, the solder of electroconductive particle can be made in electricity Effectively assemble pole part.This is because in the case where applying heat in engagement, the electrode that is formed on connecting object component with When the part of the connecting object component of surrounding them is compared, the thermal conductivity of electrode section is higher than the connecting object of electrode perimeter Thus the thermal conductivity of component part causes the heating of electrode section very fast.More than the stage of the solder melt point of electroconductive particle, lead The inside of conductive particles melts, and the oxidation overlay film for being formed in surface is not up to the fusing point (activation temperature) of fluxing agent, therefore can not Removal.In this state, since the temperature of electrode section first reaches the fusing point (activation temperature) of fluxing agent, leading on electrode The oxidation film on the surface of conductive particles is preferentially removed, and the solder in electroconductive particle can moisten diffusion on the surface.As a result, The solder of electroconductive particle can be effectively gathered on electrode.
In the 100 weight % of conductive material, the content of the fluxing agent is preferably 0.5 weight % or more, and preferably 30 Weight % is hereinafter, more preferably 25 weight % or less.The conductive material can be free of fluxing agent.The content of fluxing agent is above-mentioned When more than lower limit and below the above-mentioned upper limit, it is not easy further to form oxidation overlay film on the surface of electroconductive particle and electrode, And it is possible to further be effectively removed the oxidation overlay film for being formed in electroconductive particle and electrode surface.
(insulating properties particle)
It is highly precisely controlled from the interval the connecting object component connected by the solidfied material between conductive material Produce hair, and the viewpoint highly precisely controlled from the interval the connecting object component by being connected between weld part It sets out, the conductive material preferably comprises insulating properties particle.In the conductive material, the insulating properties particle can be not attached to The surface of the semiconductor particles.In the conductive material, the insulating properties particle preferably separates with the semiconductor particles and is existed.
The partial size of the insulating properties particle is preferably 10 μm or more, more preferably 20 μm or more, further preferably 25 μm More than, preferably 100 μm hereinafter, more preferably 75 μm hereinafter, further preferably 50 μm or less.The grain of the insulating properties particle When diameter is more than above-mentioned lower limit and below the above-mentioned upper limit, between the connecting object component connected by the solidfied material of conductive material Interval between the connecting object component that is connected of weld part further becomes suitable.
It as the material of the insulating properties particle, can enumerate: insulative resin and insulating properties inorganic matter etc..As institute Insulative resin is stated, can be enumerated: is polyolefin compound, (methyl) acrylate polymer, (methyl) acrylate copolymer, embedding Section polymer, thermoplastic resin, the cross-linking products of thermoplastic resin, heat-curing resin and water-soluble resin etc..
It as the polyolefin compound, can enumerate: polyethylene, vinyl-vinyl acetate copolymer, ethylene-acrylic acid Ester copolymer etc..As (methyl) acrylate polymer, can enumerate: poly- (methyl) methyl acrylate, (methyl) acrylic acid are poly- Ethyl ester and the poly- butyl ester of (methyl) acrylic acid etc..It as the block polymer, can enumerate: polystyrene, cinnamic acrylic ester Copolymer, SB type styrene-butadiene block copolymer, SBS type styrene-butadiene block copolymer and their hydrogenation Object etc..It as the thermoplastic resin, can enumerate: polyvinyl and ethylenic copolymer etc..As the Thermocurable Resin can be enumerated: epoxy resin, phenolic resin and melamine resin etc..It as the water-soluble resin, can enumerate: poly- second Enol, polyacrylic acid, polyacrylamide, polyvinylpyrrolidone, polyethylene oxide, methylcellulose etc..It is preferred that water-soluble tree Rouge, more preferable polyvinyl alcohol.
As the insulating properties inorganic matter, silica and organic-inorganic stuff and other stuff etc. can be enumerated.As the dioxy The particle that SiClx is formed, is not particularly limited, the particle that can be listed below: to more than two hydrolyzable alkoxy groups The silicon compound of silicyl is hydrolyzed to form cross-linking polymer particle, it is then possible to be burnt into as needed.As The organic-inorganic stuff and other stuff, for example, can enumerate: the alkoxysilyl polymer and acrylic compounds being crosslinked The organic-inorganic stuff and other stuff etc. that resin is formed.
In the 100 weight % of conductive material, the content of the insulating properties particle is preferably 0.1 weight % or more, more excellent 0.5 weight % or more, preferably 10 weight % are selected as hereinafter, more preferably 5 weight % or less.The conductive material, Ke Yihan There is the insulating properties particle.When the content of the insulating properties particle is below the lower limit and below the upper limit, by conduction material Interval between the interval for the connecting object component that the solidfied material of material is connected and the connecting object component connected by solder portion Become more appropriate.
(other compositions)
The conductive material can contain as needed, such as: coupling agent, opacifier, reactive diluent, defoaming agent, stream Flat agent, filler, incremental agent, softening agent, plasticizer, polymerization catalyst, curing catalysts, antioxidant, heat stabilizer, light are steady Determine the various additives such as agent, ultraviolet absorbing agent, lubricant, antistatic agent and fire retardant.
(manufacturing method of connection structural bodies and connection structural bodies)
Connection structural bodies of the invention includes: the first connecting object portion on the surface at least one first electrode Part, on the surface the second connecting object component at least one second electrode and by the second connecting object component With the interconnecting piece of the first connecting object component to link together.In connection structural bodies of the invention, the interconnecting piece Material includes above-mentioned electroconductive particle.In connection structural bodies of the invention, the preferably described interconnecting piece be above-mentioned electroconductive particle or Above-mentioned conductive material.In connection structural bodies of the invention, the preferably described interconnecting piece is formed by above-mentioned electroconductive particle, or by upper Conductive material is stated to be formed.In connection structural bodies of the invention, the interconnecting piece is preferably the solidfied material of the conductive material.This hair In bright connection structural bodies, the first electrode realizes electricity by the solder portion in the interconnecting piece with the second electrode Connection.
The manufacturing method of the connection structural bodies includes: using above-mentioned electroconductive particle or the conductive material, in its table Face has on the surface of the first connecting object component of at least one first electrode, and the electroconductive particle or the conduction is arranged The process of material.The manufacturing method of the connection structural bodies include: using above-mentioned electroconductive particle or the conductive material with On the opposite surface of the first connecting object component side, second connection of its surface at least one second electrode is set Object Part keeps the first electrode opposed with the second electrode.The manufacturing method of the connection structural bodies includes: will be described Conductive material is heated to the fusing point of the electroconductive particle or more, is formed and is connected by the electroconductive particle and the conductive material The interconnecting piece of the connection first connecting object component and the second connecting object component is connect, and by the interconnecting piece Solder portion process that the first electrode and the second electrode are electrically connected.It is preferred that the conductive material is heated to It is more than the solidification temperature of the Thermocurable compound.
In the manufacturing method of connection structural bodies and connection structural bodies of the invention, specific electroconductive particle or spy are used Fixed conductive material, therefore, electroconductive particle are easy to be gathered between first electrode and second electrode, and can effectively by Electroconductive particle is set on electrode (line).In addition, a part of electroconductive particle is not easy to be set to the region of not formed electrode In (space), the amount for the electroconductive particle being set in the region of not formed electrode can be substantially reduced.It is thus possible to improve the Conducting reliability between one electrode and second electrode.Furthermore it is possible to prevent the laterally adjacent interelectrode electricity that should not be connected Connection, can be improved insulating reliability.
In addition, substantially reducing in order to which effectively the solder of electroconductive particle is set on electrode and being set to not formed electricity The amount of solder in the region of pole, the conductive material it is preferable to use conductive paste rather than conductive film.
The thickness of interelectrode solder portion is preferably 10 μm or more, more preferably 20 μm or more, preferably 100 μm hereinafter, More preferably 80 μm or less.Solder area on electrode surface is (with the solder contact in the 100% of the exposed area of electrode Area) be preferably 50% or more, more preferably 70% or more, and preferably 100% or less.
In the manufacturing method of connection structural bodies of the invention, the process and formation of the second connecting object component are set In the process of the interconnecting piece, preferably apply described second without pressurization, Xiang Suoshu electroconductive particle or the conductive material The weight of connecting object component.In addition, in the process that the second connecting object component is arranged and forming the interconnecting piece In process, preferably do not apply the weight more than the second connecting object component to the electroconductive particle or the conductive material Moulding pressure.In such a case it is possible to further improve the uniformity of the amount of solder of multiple solder portions.And it is possible to more Effectively further thicken the thickness of solder portion, multiple electroconductive particles are readily collected between electrode, can be by multiple conductions Property particle is further effectively arranged on electrode (line).In addition, being not easy for a part of multiple electroconductive particles to be set to In the region (space) of not formed electrode, the electric conductivity being set in the region of not formed electrode can be effectively further reduced The amount of particle.Therefore, it can be further improved the conducting reliability between electrode.And it can further prevent should not connecting Laterally adjacent interelectrode electrical connection, can be further improved insulating reliability.
In addition, if being easy according to the coating weight of conductive paste to interconnecting piece using conductive paste without the use of conductive film And the thickness of solder portion is adjusted.On the one hand, in the case where conductive film, there are the following problems: in order to be altered or modified The thickness of interconnecting piece needs to prepare the conductive film of different-thickness or prepares the conductive film with specified thickness.In addition, with conduction Paste is compared, and conductive film cannot sufficiently reduce the melt viscosity of conductive film, there are conductions under the fusion temperature of electroconductive particle The aggregation of solder in property particle is easy interrupted tendency.
Specific embodiments of the present invention are illustrated next, with reference to attached drawing.
Fig. 1 is the section for schematically showing the connection structural bodies obtained using the conductive material of the 1st aspect of the present invention Figure.
Connection structural bodies 1 shown in FIG. 1 connects including the first connecting object component 2, the second connecting object component 3, by first Connect the interconnecting piece 4 that object Part 2 and the second connecting object component 3 link together.Interconnecting piece 4 is formed by above-mentioned conductive material. In present embodiment, the conductive material includes Thermocurable compound, Thermocurable agent and electroconductive particle.In the present embodiment In, use conductive paste as conductive material.
The solder portion 4A and Thermocurable compound that there are interconnecting piece 4 multiple electroconductive particles to assemble and be interconnected Carry out solidfied material portion 4B obtained from heat cure.
First connecting object component 2 has multiple first electrode 2a on surface (upper surface).Second connecting object component 3 There are multiple second electrode 3a on surface (lower surface).First electrode 2a and second electrode 3a realizes electricity by weld part 4A Connection.Therefore, the first connecting object component 2 and the second connecting object component 3, which pass through solder portion 4, realizes electrical connection.It needs It is bright, in interconnecting piece 4, the region different from the solder portion 4A assembled between first electrode 2a and second electrode 3a (Gu The compound portion part 4B) in be not present electroconductive particle.In the region (solidified portion 4B part) different from solder portion 4A, it is not present The electroconductive particle separated with solder part 4A.As long as it should be noted that a small amount of, be gathered in first electrode 2a and the In solder portion 4A between two electrode 3a different regions (the solidfied material portion part 4B), may exist electroconductive particle.
As shown in Figure 1, multiple electroconductive particles are gathered in first electrode 2a and second electrode 3a in connection structural bodies 1 Between, and after the melting of multiple electroconductive particles, the fusant of electroconductive particle moistens at the electrode surface to be spread and solidifies, Form solder portion 4A.Therefore, the connection area between solder portion 4A and first electrode 2a and solder portion 4A and second electrode 3a Increase.Conducting reliability and the connection reliability in connection structural bodies 1 are improved as a result,.It should be noted that in conductive material When comprising fluxing agent, usually inactivate fluxing agent gradually by heating.
It should be noted that solder portion 4A is integrally located at first electrode 2a, the second electricity in connection structural bodies 1 shown in FIG. 1 Opposed region between the 3a of pole.In the connection structural bodies 1X of variation shown in Fig. 3, only interconnecting piece 4X connects with shown in Fig. 1 It is different to connect structural body 1.Interconnecting piece 4X includes solder portion 4XA and solidfied material portion 4XB.Such as connection structural bodies 1X, most of solder portion 4XA is located in the opposed region first electrode 2a, second electrode 3a, and a part of solder portion 4XA from first electrode 2a and It is overflowed to side in the opposed region of second electrode 3a.It is overflowed to side in the region opposite from first electrode 2a, second electrode 3a Solder portion 4XA be solder portion 4XA a part, be not from solder portion 4XA be detached from electroconductive particle.It should be noted that In present embodiment, it is possible to reduce the amount of the electroconductive particle separated from solder, but the electroconductive particle being detached from solder portion can To be present in solidfied material portion.
When reducing the usage amount of electroconductive particle, it is easy to get connection structural bodies 1.Increase the usage amount of electroconductive particle When, it is easy to get connection structural bodies 1X.
In connection structural bodies 1,1X, along first electrode 2a, interconnecting piece 4,4X and second electrode 3a stacking direction, Observe the opposed part first electrode 2a and second electrode 3a, the face of preferably first electrode 2a and the opposed part second electrode 3a 50% or more in product 100%, solder portion 4A, 4XA of setting interconnecting piece 4,4X.Solder portion 4A, 4XA in interconnecting piece 4,4X is full The above-mentioned preferred embodiment of foot, to further improve conducting reliability.
Preferably along the stacking direction of the first electrode, the interconnecting piece and the second electrode, described the is observed When one electrode and the second electrode, in the first electrode and opposed 100% area of part of the second electrode 50% More than, the solder portion that is provided in the interconnecting piece.More preferably along the first electrode, the interconnecting piece and described second The stacking direction of electrode, when observing the first electrode and the second electrode, the first electrode and the second electrode pair 60% or more in 100% area of part set, the solder portion being provided in the interconnecting piece.And preferably along described first The stacking direction of electrode, the interconnecting piece and the second electrode observes the first electrode and the second electrode, described 70% or more in first electrode and opposed 100% area of part of the second electrode, the weldering being provided in the interconnecting piece Material portion.Particularly preferably along the stacking direction of the first electrode, the interconnecting piece and the second electrode, described the is observed One electrode and the second electrode, in the first electrode and opposed 100% area of part of the second electrode 80% with On, the solder portion that is provided in the interconnecting piece.Most preferably in the first electrode, the interconnecting piece and the second electrode Stacking direction on, observe the first electrode and the second electrode, the first electrode and the second electrode are opposed 90% or more in 100% area of part, the solder portion being provided in the interconnecting piece.Solder portion in the interconnecting piece meets When the preferred embodiment, conducting reliability can be further improved.
Preferably along the direction vertical with the first electrode, the interconnecting piece, the stack direction of the second electrode, see When examining the first electrode and the second electrode, described in the opposed part setting of the first electrode and the second electrode 60% or more of solder portion in interconnecting piece.More preferably along with the first electrode, the interconnecting piece, the second electrode The vertical direction of stack direction, when observing the first electrode and the opposed part of the second electrode, described first Electrode and second electrode part opposite each other are provided with 70% or more of the solder portion in the interconnecting piece.And it is preferred that Along the direction vertical with the first electrode, the interconnecting piece, the stack direction of the second electrode, first electricity is observed When pole and the second electrode, the opposed part of the first electrode and the second electrode is provided with the interconnecting piece In solder portion 90% or more.Particularly preferably along with the first electrode, the interconnecting piece, the second electrode lamination The vertical direction in direction, when observing the first electrode and the opposed part of the second electrode, in the first electrode Opposed part is provided with 95% or more of the solder portion in the interconnecting piece with the second electrode.Most preferably along with it is described First electrode, the interconnecting piece, the second electrode the vertical direction of stack direction, observe the first electrode and described When the part of two electrode contrapositions, the weldering in the interconnecting piece is set in the first electrode and the second electrode opposed part 99% or more of material portion.When solder portion in the interconnecting piece meets the preferred embodiment, conducting can be further improved Reliability.
Then, to one of the method for the conductive material manufacture connection structural bodies 1 used in one embodiment of the present of invention Example is illustrated.
Firstly, preparing the first connecting object component 2 on its surface (upper surface) with first electrode 2a.Then, such as Shown in Fig. 2 (a), setting includes Thermocurable ingredient 11B and multiple electroconductive particles on the surface of the first connecting object component 2 The conductive material 11 (first step) of 11A.The conductive material 11 used include Thermocurable compound and Thermocurable agent as Thermocurable ingredient 11B.
Conductive material 11 is set to being provided on the surface of first electrode 2a of the first connecting object component 2.Setting is conductive After material 11, electroconductive particle 11A is set on first electrode 2a (line) and the region (space) of not formed first electrode 2a On.
Setting method as conductive material 11 is not particularly limited, and can enumerate the coating by distributor progress, silk screen Printing and the spraying etc. for passing through ink discharge device.
In addition, preparing the second connecting object component 3 on its surface (lower surface) with second electrode 3a.Then, such as Shown in Fig. 2 (b), in the conductive material 11 on the surface of the first connecting object component 2, conductive material 11 is connect pair with first As 2 side opposite side of component surface on, be arranged the second connecting object component 3 (the second step).On the surface of conductive material 11, From the side second electrode 3a, the second connecting object component 3 is set.At this point, keeping first electrode 2a and second electrode 3a opposed.
Then, conductive material 11 is heated to the fusing point of electroconductive particle 11A or more (the third step).It is preferred that by conduction material Material 11 is heated to the solidification temperature of Thermocurable ingredient 11B (Thermocurable compound) or more.When heating, it is present in not formed electricity Electroconductive particle 11A in the region of pole is gathered between first electrode 2a and second electrode 3a (self-coagulation effect).Using leading When electric paste is without the use of conductive film, electroconductive particle 11A is further effectively gathered in first electrode 2a and second electrode Between 3a.In addition, electroconductive particle 11A is melted and is interconnected.In addition, Thermocurable ingredient 11B carries out heat cure.As a result, As shown in Fig. 2 (c), the interconnecting piece 4 of the first connecting object component 2 and the second connecting object component 3 is connected by 11 shape of conductive material At.Interconnecting piece 4 is formed by conductive material 11, and solder portion 4A is engaged by multiple electroconductive particle 11A and formed, solidfied material portion 4B Heat cure is carried out by Thermocurable ingredient 11B to be formed.If electroconductive particle 11A is sufficiently moved, it is not located at first electrode Electroconductive particle 11A between 2a and second electrode 3a starts to move, until electroconductive particle 11A be moved to first electrode 2a and Mobile completion between second electrode 3a, can not keep temperature constant.
In the present embodiment, the semiconductor particles in the first step and the second step, in electroconductive particle 11A Solder and electroconductive particle 11A covering portion in include silver without alloying.Therefore, it heats and leads in the third step When electric material 11, it can be heated to the melting temperature of semiconductor particles or more, electroconductive particle 11A can be at relatively low temperatures Melting, can form solder portion 4A at relatively low temperatures.In addition, in the present embodiment, multiple electroconductive particle 11A connect Close and formed solder portion 4A in, in the solder of the semiconductor particles in electroconductive particle 11A and the covering portion of electroconductive particle 11 The silver for including carries out alloying.Therefore, the fusing point of solder portion 4A can be made to be higher than the fusing point of semiconductor particles, and can be effectively Improve the impact resistance of solder portion 4A.
In present embodiment, without pressurization preferably in the second step and the third step.In this case, Apply the weight of the second connecting object component 3 to conductive material 11.Therefore, when forming interconnecting piece 4, electroconductive particle 11A is more It is effectively further gathered between first electrode 2a and second electrode 3a.It should be noted that if in the second step and institute It states and pressurizes at least one process of the third step, then electroconductive particle 11A attempts to be gathered in first electrode 2a and second The tendency that effect between electrode 3a is obstructed improves.
In addition, in present embodiment, due to without pressurization, the first connecting object component of applying conductive material and second When connecting object component is overlapped, even if there are in the state of deviation, can also correct partially in first electrode and second electrode alignment Difference connects first electrode and second electrode (autoregistration effect).Itself the reason is as follows that: had occurred between first electrode and second electrode The fusion welding of self aggregation, the area that the solder between first electrode and second electrode is contacted with the other compositions of conductive material are minimum When energy stabilization, therefore become that contact area is minimum and the power of connection structure calibrated in action.At this point, expectation Conductive material will not solidify, and under the temperature and time, the viscosity foot of the ingredient other than the electroconductive particle of conductive material It is enough low.
As described above, obtaining connection structural bodies 1 shown in Fig. 1.It should be noted that described second can be carried out continuously Process and the third step.In addition, after carrying out the second step, can by the first obtained connecting object component 2, lead The laminated body of electric material 11 and the second connecting object component 3 is moved to heating part, carries out the third step.To carry out described add The laminated body can be set on heating element by heat, the laminated body can also be set in the space of heating.
The heating temperature in the third step is preferably 140 DEG C or more, and more preferably 160 DEG C or more, preferably 450 DEG C hereinafter, more preferably 250 DEG C hereinafter, further preferably 200 DEG C or less.
It as the heating means of the third step, can enumerate: heat connection structural bodies by using reflow ovens or baking oven It is whole, the method for being heated to the solidification temperature of the fusing point of electroconductive particle or more and Thermocurable compound or more or only office The method that portion the interconnecting piece of connection structural bodies is heated.
It as the utensil for local heating methods, can enumerate: heating plate, the heat gun with hot wind, soldering iron and infrared Heater etc..
In addition, when carrying out local heating with heating plate, by the high metal of thermal conductivity, other unexcellent immediately below interconnecting piece The position of heating is selected to form the upper surface of heating plate preferably by the material of the low heat conductivities such as fluororesin.
The first connecting object component, there is no particular restriction for the second connecting object component.As first connection pair As component, the second connecting object component, specifically, can enumerate: semiconductor chip, semiconductor packages, LED chip, LED envelope The electronic components such as dress, capacitor and diode；And resin film, printing plate, flexible printed board, flexible flat base, rigidity are flexible Electronic components such as the circuit board of substrate, glass epoxy substrate and glass substrate etc. etc..The first connecting object component, second connect Connecing object Part is preferably electronic component.
It is preferred that at least one connecting object portion in the first connecting object component and the second connecting object component Part is resin film, flexible print wiring board, flexible flat cable or rigidity flexible.It is preferred that the second connecting object component For resin film, flexible printed board, flexible flat cable or rigid flex plate.Resin film, flexible print wiring board, flexible flat wire Cable and rigid flexible electric circuit board have the characteristic of high-flexibility and relative lightweight.Conductive film is used for the connection of connecting object component When, there are the solders of electroconductive particle to be difficult to be gathered in the tendency on electrode.In this regard, by using conductive paste, even if using Resin film, flexible printed board, flexible flat cable or rigid flex plate, the solder of electroconductive particle can also effectively be assembled On the electrode, interelectrode conducting reliability is sufficiently improved.Use resin film, flexible printed board, flexible flat cable or rigidity In the case where flex plate, compared with the case where using other connecting object components such as semiconductor chip, can without pressurization, and Further effectively it is improved the effect of interelectrode conducting reliability.
As the electrode for being set to the connecting object component, can enumerate: gold electrode, nickel electrode, tin electrode, aluminium electrode, The metal electrodes such as copper electrode, molybdenum electrode, silver electrode, SUS electrode and tungsten electrode.The connecting object component is flexible print wiring When plate, the preferably described electrode is gold electrode, nickel electrode, tin electrode, silver electrode or copper electrode.The connecting object component is glass In the case where substrate, the electrode is preferably aluminium electrode, copper electrode, molybdenum electrode, silver electrode or tungsten electrode.It should be noted that In the case that the electrode is aluminium electrode, the electrode only formed by aluminium can be, be also possible to aluminium layer and be stacked on metal oxide Surface and the electrode that is formed.As the material of the metal oxide layer, can enumerate including doped with trivalent metallic element Indium oxide and zinc oxide etc. doped with trivalent metallic element.As the trivalent metallic element, Sn, Al, Ga etc. can be enumerated.
In connection structural bodies of the invention, the preferably described first electrode and the second electrode are set to area array or outer In enclosing.In the case that the first electrode and the second electrode are set in area array or periphery, can further have Effect ground plays effect of the invention.The area array refers to that such as flowering structure, electrode is set to connecting object component with clathrate It is provided on the surface of electrode.The periphery refers to that electrode is set to the structure of the peripheral part of connecting object component.In electrode arrangement In the case where at pectinate texture, as long as the solder in electroconductive particle is assembled along the direction perpendicular to pectination, in this regard, in institute It states in area array or peripheral structure, on the surface for being provided with electrode, the solder of electroconductive particle needs comprehensively and equably Cohesion.Therefore, in the conventional method, the amount of solder is easy uneven, in this regard, in method of the invention, the weldering of electroconductive particle Material can be further effectively arranged on electrode, and the solder of electroconductive particle can agglomerate comprehensively and equably.
Hereafter, reference implementation mode and comparative example are illustrated into the present invention.The present invention is not limited to following embodiments.
Thermocurable compound:
Thermocurable compound 1: resorcinol type ring oxygen compound, Kyoeisha Chemical Co., Ltd. manufacture " Epolight TDC-LC ", epoxide equivalent: 120g/eq
Thermocurable compound 2: " EP-3300 ", the epoxide equivalent that epoxide, ADEKA company manufacture: 160g/eq
Thermal curing agents:
" the Fuji Cure 7000 " of latency epoxy thermosetting agent 1:T&K TOKA company manufacture
" HXA-3922HP " of latency epoxy thermosetting agent 2:Asahi Kasei E-Materials Co., Ltd. manufacture
Fluxing agent:
Fluxing agent 1: " glutaric acid " of Wako Pure Chemical Industries, Ltd.'s manufacture
Electroconductive particle:
(SnBi semiconductor particles, use the " Sn manufactured to Co., Ltd., Mitsui Metal Co., Ltd. at 139 DEG C of fusing point to electroconductive particle 1 42Bi 58 " carries out the semiconductor particles of selection, and electroconductive particle, the partial size of covering portion: 31 μm, cladding are formed by electroless plating The thickness in portion: 0.5 μm)
(manufacturing method of electroconductive particle 1)
With the electroconductive particle for being formed with covering portion by electroless plating:
The semiconductor particles that the partial size of 50g is 30 μm are put into the 1 weight % citric acid solution of 500g, to remove semiconductor particles Oxidation film on surface.The solution containing 5g silver nitrate and 1000g ion exchange water is prepared, and 50g is added to the solution and removes The semiconductor particles of oxidation film are simultaneously mixed, and suspension is obtained.Into obtained suspension add 30g thiomalic acid, 80gN- acetyl imidazole, 10g sodium hypophosphite simultaneously mix, and obtain plating solution.It will be resulting by using the ammonia solution of 10 weight % The pH of plating solution is adjusted to 9, implements 20 minutes electroless platings at 25 DEG C, obtains being formed with packet from there through electroless plating Cover the electroconductive particle in portion.
(" the Sn that SnBi semiconductor particles, 139 DEG C of fusing point, selection are manufactured using Co., Ltd., Mitsui Metal Co., Ltd. of electroconductive particle 2 58 " semiconductor particles of 42Bi, electroconductive particle, the partial size of the metal portion and covering portion that are formed by electroless plating: 33 μm, The thickness of metal portion: 1 μm, the thickness of covering portion: 0.5 μm)
(manufacturing method of electroconductive particle 2)
Electroconductive particle with the metal portion and covering portion that are formed by electroless plating:
The semiconductor particles that 50g partial size is 30 μm are put into the 1 weight % citric acid solution of 500g, to remove semiconductor particles table Oxidation film on face.The semiconductor particles that oxide film dissolving is removed using 50g are adhered to palladium by double ingredient activation methods, are obtained in table The semiconductor particles of palladium are attached on face.The solution containing 20g nickel sulfate and 1000g ion exchange water is prepared, and by 30g on surface On be attached with the semiconductor particles of palladium and be added in the solution and mix, obtain the first suspension.Add into the first obtained suspension Enter 30g citric acid, 80g sodium hypophosphite and 10g acetic acid and mix, obtains the first plating solution.By using 10 weight % ammonium salt solutions The pH of the first obtained plating solution is adjusted to 10, implements 20 minutes electroless platings at 60 DEG C, obtains passing through electroless plating It is formed with the electroconductive particle of metal portion.
Then, the solution containing 5g silver nitrate and 1000g ion exchange water is prepared, the electric conductivity of the metal portion will be formed with Particle 50g is added the solution and mixes, and obtains the second suspension.Into the second obtained suspension be added 30g succinimide, 80gN- acetyl imidazole, 5g glyoxalic acid simultaneously mix, and obtain the second electroplate liquid.It will be obtained by using 10 weight % ammonia solutions The pH of second plating solution is adjusted to 9, implements 20 minutes electroless platings at 20 DEG C, obtains forming metal portion by electroless plating With the electroconductive particle of covering portion.
(SnBi semiconductor particles, use what is manufactured to Co., Ltd., Mitsui Metal Co., Ltd. at 139 DEG C of fusing point to electroconductive particle 3 The semiconductor particles that " Sn42Bi58 " is selected pass through the electroconductive particle for the covering portion that electroless plating is formed with, grain Diameter: 32 μm, the thickness of covering portion: 1 μm)
(manufacturing method of electroconductive particle 3)
The electroconductive particle of covering portion is formed by being electrolysed plating:
The semiconductor particles that 50g partial size is 30 μm are put into the 1 weight % citric acid solution of 500g, to remove semiconductor particles table Oxidation film on face.Prepare containing 5g silver nitrate, 1000g ion exchange water, 5g the bromo- 5,5- dimethyl hydantoin of 1,3- bis- With the solution of 3g thiomalic acid, and the 50g semiconductor particles for having removed oxidation film are put into the solution and are mixed, is suspended Liquid.Using obtained suspension, in anode: platinum, cathode: phosphorous copper, current density: 1A/dm2Under conditions of carry out electrolysis plating It applies, obtains the electroconductive particle for forming covering portion by being electrolysed plating.
Electroconductive particle 4 (SAC particle, 218 DEG C of fusing point, thousand " M705 ", the partial sizes that firmly metal Co., Ltd. manufactures: 30 μm)
(SnBi semiconductor particles, use what is manufactured to Co., Ltd., Mitsui Metal Co., Ltd. at 139 DEG C of fusing point to electroconductive particle 5 The semiconductor particles that " Sn42Bi58 " is selected are formed with the electroconductive particle of covering portion, its partial size by being electrolysed plating: 35 μm, the thickness of covering portion: 2.5 μm)
(manufacturing method of electroconductive particle 5)
The electroconductive particle for being formed with covering portion by being electrolysed plating:
The semiconductor particles that the partial size of 50g is 30 μm are put into the 1 weight % citric acid solution of 500g, to remove semiconductor particles Oxidation film on surface.Prepare containing 5g silver nitrate, 1000g ion exchange water, 5g the bromo- 5,5- dimethyl second of 1,3- bis- in acyl The solution of urea and 3g thiomalic acid, and the 50g semiconductor particles for having removed oxidation film are put into the solution and are mixed, it is hanged Supernatant liquid.Using obtained suspension, in anode: platinum, cathode: phosphorous copper, current density: 3A/dm2Under conditions of carry out electrolysis electricity Plating obtains the electroconductive particle that covering portion is formed by being electrolysed plating.
(manufacturing method of electroconductive particle 6)
The electroconductive particle for being formed with covering portion by being electrolysed plating:
The semiconductor particles that the partial size of 50g is 30 μm are put into the 1 weight % citric acid solution of 500g, to remove semiconductor particles Oxidation film on surface.Prepare containing 5g silver nitrate, 1000g ion exchange water, 5g the bromo- 5,5- dimethyl second of 1,3- bis- in acyl The solution of urea and 3g thiomalic acid, and the 50g semiconductor particles for having removed oxidation film are put into the solution and are mixed, it is hanged Supernatant liquid.Using obtained suspension, in anode: platinum, cathode: phosphorous copper, current density: 2A/dm2Under conditions of carry out electrolysis plating It applies, thus obtains the electroconductive particle for being formed with covering portion by being electrolysed plating.
(SnBi semiconductor particles, use the " L20- that the manufacture of metal Co., Ltd. is lived to thousand at 139 DEG C of fusing point to electroconductive particle 7 300500 " the semiconductor particles selected are formed with electroconductive particle, its partial size of covering portion: 31 μ by electroless plating M, the thickness of covering portion: 0.08 μm)
(manufacturing method of electroconductive particle 7)
The electroconductive particle of covering portion is formed with by electroless plating:
The semiconductor particles that 50g partial size is 30 μm are put into 10 weight % hydroxides of the nitrilotriacetic acid containing 1g, 50g Sodium solution stirs 5 minutes at 50 DEG C, removes the oxidation film on solder surface by washing.50g has been removed to the weldering of oxidation film Material particle is put into the solution containing 2g palladium sulfate and 100g ion exchange water, and palladium is attached on the surface of semiconductor particles.
Add 1000g ion exchange water, 10g ethylenediamine tetra-acetic acid, 10g nitrilotriacetic acid, 30g dibastic sodium phosphate, 30g hydrogen Sodium oxide molybdena, 3g silver nitrate and 1g polyethylene glycol (cetomacrogol 1000) simultaneously mix, and obtain plating solution.Use 10 weight % ammonia solutions It is adjusted, so that the pH for obtaining plating solution is 8.The 50g semiconductor particles and 6g sodium borohydride of palladium are attached with to electroplate liquid addition, Implement electroless plating 20 minutes at 25 DEG C, obtains the electroconductive particle for forming covering portion by electroless plating.
(SnBi semiconductor particles, use the " L20- that the manufacture of metal Co., Ltd. is lived to thousand at 139 DEG C of fusing point to electroconductive particle 8 300500 " the semiconductor particles selected are formed with electroconductive particle, its partial size of covering portion: 31 μ by electroless plating M, the thickness of covering portion: 0.12 μm)
(manufacturing method of electroconductive particle 8)
The electroconductive particle of covering portion is formed with by electroless plating:
The semiconductor particles that 50g partial size is 30 μm are put into the 10 weight % hydroxides containing 1g nitrilotriacetic acid and 50g It in the solution of sodium, is stirred 5 minutes at 50 DEG C, the oxidation film on solder surface is removed by washing.50g oxidation film has been removed into Semiconductor particles be put into the solution containing 2g palladium sulfate and 100g ion exchange water, so that palladium is attached to the surface of semiconductor particles On.
Add 1000g ion exchange water, 10g tetrasodium ethylenediamine tetraacetate, 10g nitrilotriacetic acid disodium, 30g phosphoric acid hydrogen Sodium, 30g sodium hydroxide, 7g methanesulfonic acid silver, 1g polyethylene glycol (cetomacrogol 1000) simultaneously mix, to obtain plating solution.By making The pH of gained plating solution is adjusted to 3 with 10 weight % sulfuric acid solutions.The 50g semiconductor particles for being attached with palladium and 6g oxalic acid are put into plating It applies in liquid, implements 20 minutes electroless platings at 25 DEG C, thus obtain the conduction for being formed with covering portion by electroless plating Property particle.
(SnBi semiconductor particles, use the " L20- that the manufacture of metal Co., Ltd. is lived to thousand at 139 DEG C of fusing point to electroconductive particle 9 300500 " the semiconductor particles selected, are formed with electroconductive particle, the partial size of covering portion by electroless plating: 31 μm, The thickness of covering portion: 0.15 μm)
(manufacturing method of electroconductive particle 9)
The electroconductive particle of covering portion is formed with by electroless plating:
The semiconductor particles that the partial size of 50g is 30 μm are put into the 10 weight % hydrogen-oxygens containing 1g nitrilotriacetic acid and 50g It in the solution for changing sodium, is stirred 5 minutes at 50 DEG C, the oxidation film on solder surface is removed by washing.50g deoxidation has been removed into The semiconductor particles of film are put into the solution containing 2g palladium sulfate and 100g ion exchange water, and palladium is made to be attached to the surface of semiconductor particles On.
Add 1000g ion exchange water, 10g tetrasodium ethylenediamine tetraacetate, 10g nitrilotriacetic acid disodium, 30g phosphoric acid hydrogen Sodium, 30g sodium hydroxide, 7g methanesulfonic acid silver, 1g polyethylene glycol (cetomacrogol 1000) simultaneously mix, and obtain electroplate liquid.By using The pH of obtained plating solution is adjusted to 7 by 10 weight % sodium hydroxide solutions.The 50g semiconductor particles and 6g grass of palladium will be attached with Acid is put into electroplate liquid, is implemented 20 minutes electroless platings at 40 DEG C, is obtained being formed with covering portion by electroless plating Electroconductive particle.
The thickness of metal portion and the thickness of covering portion:
The thickness of metal portion and the thickness of covering portion are measured by the above method.
(Examples 1 to 8 and comparative example 1)
(1) preparation of conductive material
Combined amount shown in ingredient following table 1 shown in the following table 1 is mixed, and is mixed and is disappeared with planet strrier Bubble, to obtain conductive material (anisotropic conductive paste).
(2) production of connection structure (area array substrate)
The specific manufacturing method of connection structural bodies under (2-1) condition A:
As the second connecting object component, on the surface of semiconductor chip main body (5 × 5mm of size, thickness 0.4mm), with 400 μm 250 μm of spacing of copper electrode is configured to area array, and preparation most surface be formed with passivating film (polyimides, Thickness: 5 μm, the opening diameter of electrode portion: 200 μm) semiconductor chip.The corresponding copper electrode number of one semiconductor chip is 10 A × 10 totals 100.
As the first connecting object component, following glass epoxy substrate is prepared: in the glass epoxy substrate main body (size 20 × 20mm, thickness 1.2mm, material FR-4) surface on, copper electrode is set, and itself and the second connecting object component is made to form phase Same electrode pattern, and solder mask is formed in the region of not set copper electrode.Between the surface of copper electrode and the surface of solder mask Segment difference be 15 μm, and solder mask is more prominent than copper electrode.
The conductive material just manufactured (anisotropic conductive paste) is coated on the upper surface of the glass epoxy substrate, is made It has 100 μm of thickness, forms anisotropic conductive paste layer.Then, by semiconductor chip stack in anisotropic conductive The upper surface of paste layer keeps electrode opposite each other.The weight of the semiconductor chip is applied to anisotropic conductive paste layer. It since the state, is heated, after so that the temperature of anisotropic conductive paste layer is started to warm up 5 seconds, is heated to 139 DEG C (fusing point of solder).Also, after starting to warm up 15 seconds, carrying out heating makes the temperature of anisotropic conductive paste layer reach 160 DEG C, solidify anisotropic conductive paste layer, obtains connection structural bodies.When heating, without pressurization.
The specific manufacturing method of the connection structural bodies of (2-2) at condition B:
Following change is carried out, in addition to this, connection structural bodies (area array base is manufactured in a manner of identical with condition A Plate).
The change point of condition B is changed to from condition A:
The conductive material just manufactured (anisotropic conductive paste) is coated on the upper surface of the glass epoxy substrate, is made It has 100 μm of thickness, after forming anisotropic conductive paste layer, placed 6 in the environment of 25 DEG C and 50% humidity A hour after placement, by semiconductor chip stack on the upper surface of anisotropic conductive paste layer, keeps electrode opposite each other.
(evaluation)
(1) viscosity (η 25) of the conductive material (anisotropic conductive paste) at 25 DEG C.
Using E type viscosimeter (" the TVE 22L " of Toki Sangyo Co., Ltd.'s manufacture) under conditions of 25 DEG C and 5rpm Viscosity (η 25) of the conductive material (anisotropic conductive paste) at 25 DEG C after measurement just manufacture.η is judged based on following standard 25。
[judgment criteria of η 25]
Δ: η 25 is less than 20Pas
Zero: η 25 is 20Pas or more and 600Pas or less
×: η 25 is greater than 600Pas
(2) viscosity (η mp) of the conductive material (anisotropic conductive paste) of the fusing point of electroconductive particle
Using STRESSTECH (manufacture of REOLOGICA company), in strain controlling 1rad, frequency 1Hz, the rate of heat addition 20 DEG C/min, measure 40 DEG C~electroconductive particle of temperature range fusing point under conditions of measure the conductive material just manufactured (respectively to different Property conductive paste).In the measurement, the viscosity under the fusing point of electroconductive particle is read, as leading at electroconductive particle fusing point The viscosity (η mp) of electric material (anisotropic conductive paste).η mp passes through standard determination below.
[criterion of η mp]
Δ: η mp is less than 0.1Pas
Zero: η mp is 0.1Pas or more and 5Pas or less
×: η mp is greater than 5Pas
(3) storage stability
Using E type viscosimeter (" the TVE 22L " of the manufacture of Toki Sangyo Co., Ltd.'s manufacture) in 25 DEG C and the item of 5rpm Viscosity (η 1) of the conductive material (anisotropic conductive paste) just manufactured at 25 DEG C is measured under part.In addition, with identical as η 1 Mode measure placed 3 days under 25 DEG C and 50% humidity after viscosity of the conductive material (anisotropic conductive paste) at 25 DEG C (η2).Storage stability is judged according to following standard.
[judgment criteria of storage stability]
Zero: η 2/ η 1 is less than 2
Δ: 2/ η 1 of η is 2 more than and less than 3
×: 2/ η 1 of η is 3 or more
(4) wetability of solder
According to above-mentioned (3) evaluation preparation placed 3 days under conditions of 25 DEG C, humidity 50% after conductive material (respectively to Anisotropic conductive paste).Using these conductive materials (anisotropic conductive paste), the wetability of solder is assessed.The wetting of solder Property assessment it is as follows.The wetability of solder is judged according to following standard.
The evaluation method of solder wettability:
2mg conductive material (anisotropic conductive paste) is coated on the 8mm with 2mm φ mask2On gold electrode, it is used in combination Hot plate heats 10 minutes at 170 DEG C.Then, in image analysis, the ratio (weldering of the wetting zones and gold electrode of solder is calculated Expect the region contacted with the surface of gold electrode).
[the wetability judgment criteria of solder]
Zero: solder is 70% or more relative to the ratio of the wetting areas of gold electrode
△: solder is 40% more than and less than 70% relative to the ratio of the wetting areas of gold electrode
×: solder relative to the wetting areas of gold electrode ratio less than 40%
(5) on electrode solder setting precision
In the connection structural bodies obtained at condition A and B, along first electrode, interconnecting piece, second electrode lamination side To, when observing the opposed part of first electrode and second electrode, the area of the part opposed to first electrode and second electrode The ratio X of the area of the solder portion in interconnecting piece is provided in 100%.Setting based on following standard determination solder on the electrode Precision.
[the judgement benchmark of the setting precision of solder on electrode]
00: ratio X is 70% or more
Zero: ratio X is 60% more than and less than 70%
Δ: ratio X is 50% more than and less than 60%
×: ratio X is less than 50%
(6) the conducting reliability between upper/lower electrode
In the connection structural bodies (n=15) obtained at condition A and B, measured respectively by four-terminal method upper/lower electrode it Between unit tie point connection resistance.Calculate the average value of connection resistance.It should be noted that according to voltage=electric current × electricity The relationship of resistance, voltage when by measurement constant current flowing acquire connection resistance.It is reliable based on the judgement conducting of following standard Property.
[judgment criteria of conducting reliability]
00: the average value for connecting resistance is 50m Ω or less
Zero: the average value for connecting resistance is greater than 50m Ω and is 70m Ω or less
Δ: the average value for connecting resistance is greater than 70m Ω and is 100m Ω or less
×: the average value for connecting resistance is more than 100m Ω or generation bad connection
(7) insulating reliability between adjacent electrode
In the connection structural bodies (n=15) obtained at condition A and B, put in the atmosphere of 85 DEG C and humidity 85% After setting 100 hours, apply 5V between adjacent electrodes, resistance value is measured at 25.Insulating reliability is judged based on following standard.
[criterion of insulating reliability]
00: the average value for connecting resistance is 107Ω or more
Zero: the average value for connecting resistance is 106Ω is more than and less than 107Ω
Δ: the average value for connecting resistance is 105Ω is more than and less than 106Ω
×: the average value of resistance is connected less than 105Ω
(8) impact resistance
Prepare the connection structural bodies for evaluating above-mentioned (6).These connection structural bodies are fallen from the position of height 70cm, are led to It crosses and confirms conducting reliability in a manner of identical with the evaluation of above-mentioned (6) to evaluate impact resistance.Based on following standard, from described (6) increment rate of the resistance value of the average value of resistance is connected obtained in evaluation to judge impact resistance.
[judgment criteria of impact resistance]
00: resistance value is 20% or less relative to the increment rate of the average value of connection resistance
Zero: resistance value is greater than 20% relative to the increment rate of the average value of connection resistance and is 35% or less
△: resistance value is greater than 35% relative to the increment rate of the average value of connection resistance and is 50% or less
×: the resistance value increment rate of connection resistance average value is greater than 50%
(9) clad ratio
Obtained electroconductive particle is calculated in the 100% of the surface area entirety of semiconductor particles in the solder The surface area (clad ratio) covered on particle surface by covering portion.Pass through the SEM-EDX electroconductive particle analyzed and analysis Image calculates clad ratio by carrying out Ag mapping.Clad ratio is judged according to following standard.
[judgment criteria of clad ratio]
00: coverage rate is greater than 95%
Zero: coverage rate is greater than 90% and is 95% or less
△: coverage rate is greater than 80% and is 90% or less
×: coverage rate is 80% or less
As a result as shown in table 1 below.
[table 1]
Even if using flexible printed board, resin film, flexible flat cable and rigid flex plate, also observable To identical tendency.

Claims (14)

1. a kind of electroconductive particle, has:
Fusing point is lower than 200 DEG C of semiconductor particles, and
The covering portion being set on the surface of the semiconductor particles, wherein
The covering portion contains silver.
2. electroconductive particle according to claim 1, wherein the semiconductor particles contain tin and bismuth.
3. electroconductive particle according to claim 1 or 2, wherein
In 100 weight % electroconductive particles, the silver content is 1 weight % or more and 20 weight % or less.
4. electroconductive particle according to any one of claims 1 to 3, wherein
In the surface area whole 100% of the semiconductor particles, by being covered by the covering portion in the surface of the semiconductor particles Surface area be 80% or more.
5. electroconductive particle described according to claim 1~any one of 4, wherein
The covering portion with a thickness of 0.1 μm or more and 5 μm or less.
6. electroconductive particle described according to claim 1~any one of 5, wherein the outer surface of the semiconductor particles and Has nickeliferous metal portion between the covering portion.
7. a kind of conductive material contains electroconductive particle and Thermocurable described in any one of claim 1~6 Compound.
8. conductive material according to claim 7, wherein in 100 weight % of conductive material, the electroconductive particle contains Amount is more than 50 weight %.
9. conductive material according to claim 7 or 8, wherein the Thermocurable compound contains with polyether skeleton Thermocurable compound.
10. the conductive material according to any one of claim 7~9, containing fusing point be 50 DEG C or more and 140 DEG C with Under fluxing agent.
11. the conductive material according to any one of claim 7~10, the viscosity at 25 DEG C be 20Pas with Upper and 600Pas or less.
12. the conductive material according to any one of claim 7~11 is conductive paste.
13. a kind of connection structural bodies, has:
Surface has the first connecting object component of at least one first electrode,
Surface has the second connecting object component of at least one second electrode, and
The interconnecting piece that the first connecting object component and second connection link together to component,
Wherein, the material of the interconnecting piece contains electroconductive particle described in any one of claim 1~6,
The first electrode and the second electrode realize electrical connection by the solder portion in the interconnecting piece.
14. connection structural bodies according to claim 13, wherein along the first electrode, the interconnecting piece and described The stack direction of second electrode, when observing the first electrode part opposite with the second electrode, the first electrode 50% or more in the area 100% of the part opposite with the second electrode is configured with the solder portion in the interconnecting piece.
CN201880004430.7A 2017-03-23 2018-03-20 Electroconductive particle, conductive material and connection structural bodies Pending CN109983544A (en)

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