CN113519031B - Conductive particle, conductive material, and connection structure - Google Patents
Conductive particle, conductive material, and connection structure Download PDFInfo
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- CN113519031B CN113519031B CN202080017319.9A CN202080017319A CN113519031B CN 113519031 B CN113519031 B CN 113519031B CN 202080017319 A CN202080017319 A CN 202080017319A CN 113519031 B CN113519031 B CN 113519031B
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- 238000004544 sputter deposition Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 1
- 229910000597 tin-copper alloy Inorganic materials 0.000 description 1
- 229910001174 tin-lead alloy Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- XYJRNCYWTVGEEG-UHFFFAOYSA-N trimethoxy(2-methylpropyl)silane Chemical compound CO[Si](OC)(OC)CC(C)C XYJRNCYWTVGEEG-UHFFFAOYSA-N 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- LGROXJWYRXANBB-UHFFFAOYSA-N trimethoxy(propan-2-yl)silane Chemical compound CO[Si](OC)(OC)C(C)C LGROXJWYRXANBB-UHFFFAOYSA-N 0.000 description 1
- GRPURDFRFHUDSP-UHFFFAOYSA-N tris(prop-2-enyl) benzene-1,2,4-tricarboxylate Chemical compound C=CCOC(=O)C1=CC=C(C(=O)OCC=C)C(C(=O)OCC=C)=C1 GRPURDFRFHUDSP-UHFFFAOYSA-N 0.000 description 1
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 229920006163 vinyl copolymer Polymers 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
- H01B5/16—Non-insulated conductors or conductive bodies characterised by their form comprising conductive material in insulating or poorly conductive material, e.g. conductive rubber
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
- H01R11/00—Individual connecting elements providing two or more spaced connecting locations for conductive members which are, or may be, thereby interconnected, e.g. end pieces for wires or cables supported by the wire or cable and having means for facilitating electrical connection to some other wire, terminal, or conductive member, blocks of binding posts
- H01R11/01—Individual connecting elements providing two or more spaced connecting locations for conductive members which are, or may be, thereby interconnected, e.g. end pieces for wires or cables supported by the wire or cable and having means for facilitating electrical connection to some other wire, terminal, or conductive member, blocks of binding posts characterised by the form or arrangement of the conductive interconnection between the connecting locations
Landscapes
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Conductive Materials (AREA)
- Non-Insulated Conductors (AREA)
Abstract
The invention provides conductive particles, which can effectively reduce the connection resistance between electrodes and can also effectively inhibit aggregation between conductive particles. The conductive particles (1, 11, 21) according to the present invention are provided with: a base particle (2) containing a conductive metal inside the base particle, and conductive portions (3, 12, 22) disposed on the surface of the base particle.
Description
Technical Field
The present invention relates to conductive particles having conductive portions disposed on the surfaces of base particles. The present invention also relates to a conductive material and a connection structure using the conductive particles.
Background
Anisotropic conductive materials such as anisotropic conductive pastes and anisotropic conductive films are widely known. In the anisotropic conductive material, conductive particles are dispersed in a binder resin. As the conductive particles, there are also used conductive particles including base particles and conductive portions arranged on the surfaces of the base particles.
The anisotropic conductive material described above is used to obtain various connection structures. Examples of the connection structure using the anisotropic conductive material include a connection (FOG (Film on Glass)) between a flexible circuit board and a glass substrate, a connection (COF (Chip on Film)) between a semiconductor chip and a flexible circuit board, a connection (COG (Chip on Glass)) between a semiconductor chip and a glass substrate, and a connection (FOB (Film on Board)) between a flexible circuit board and a glass epoxy substrate.
As an example of the conductive particles, patent document 1 described below discloses a conductive particle including: a nickel layer, and a gold layer formed on the nickel layer. The average film thickness of the gold layer isThe following is given. In the conductive particles, the gold layer is the outermost layer. Meanwhile, in the conductive particles, the elemental composition ratio (Ni/Au) of nickel and gold on the surface of the conductive particles, which was obtained by X-ray photoelectron spectroscopy analysis, was 0.4 or less.
Patent document 2 discloses a conductive particle comprising: core particles, ni plating, noble metal plating, and rust inhibitive film. The Ni plating Bao Fushang is a core particle. At least a part of the Ni plating layer is the noble metal plating layer Bao Fushang. The noble metal plating layer contains at least one of Au and Pd. The rust preventive film includes at least one of the Ni plating layer and the noble metal plating layer. The rust inhibitive film contains an organic compound.
Prior art literature
Patent literature
Patent document 1, japanese patent application laid-open No. 2009-102731
Patent document 2 Japanese patent application laid-open No. 2013-20721
Disclosure of Invention
Problems to be solved by the invention
In recent years, in a conductive material containing conductive particles, the conductive particles have been reduced in particle size due to finer pitches of wirings, connectors, and the like in printed wiring boards and the like.
When connecting electrodes using conductive particles having a small particle diameter to prepare a connection structure, the thickness of the conductive portion in the conductive particles may be increased in order to sufficiently reduce the connection resistance between the electrodes in the vertical direction. However, if the thickness of the conductive portion is increased, aggregation may occur between conductive particles when the conductive portion is formed by plating. If the conductive particles are aggregated, the electrodes adjacent to each other in the lateral direction tend to be easily connected, and it is difficult to improve the insulation reliability between the electrodes adjacent to each other in the lateral direction.
Meanwhile, if the conductive portion is thinned to suppress aggregation between conductive particles, aggregation between conductive particles can be suppressed when the conductive portion is formed by plating, but it is difficult to sufficiently reduce the connection resistance between the electrodes in the up-down direction. In the conventional conductive particles, it is difficult to reduce the connection resistance between electrodes and to suppress aggregation between conductive particles.
The purpose of the present invention is to provide conductive particles that can effectively reduce the connection resistance between electrodes and can also effectively inhibit aggregation between conductive particles. The present invention also provides a conductive material and a connection structure using the conductive particles.
Technical scheme for solving problems
According to a broad aspect of the present invention, there is provided a conductive particle comprising: the conductive material comprises a base particle and a conductive part arranged on the surface of the base particle, wherein the base particle contains conductive metal inside the base particle.
According to a specific aspect of the conductive particle according to the present invention, the porosity of the base material particle is 10% or more.
According to a specific aspect of the conductive particles according to the present invention, the conductive metal contains nickel, gold, palladium, silver or copper.
According to a specific aspect of the conductive particle according to the present invention, the conductive portion contains nickel, gold, palladium, silver, or copper.
According to a specific aspect of the conductive particles according to the present invention, the conductive particles have a 10% K value of 100N/mm 2 or more and 25000N/mm 2 or less.
According to a specific aspect of the conductive particles according to the present invention, the conductive particles have a 30% K value of 100N/mm 2 or more and 15000N/mm 2 or less.
According to a specific aspect of the conductive particle according to the present invention, the ratio of the 10% k value of the conductive particle to the 30% k value of the conductive particle is 1.5 or more and 5 or less.
According to a specific aspect of the conductive particles according to the present invention, the conductive particles have a particle diameter of 0.1 μm or more and 1000 μm or less.
According to a specific aspect of the conductive particle according to the present invention, the content of the conductive metal contained in the base particle is 0.1% by volume or more and 30% by volume or less in 100% by volume of the conductive particle.
According to a specific aspect of the conductive particle according to the present invention, the conductive particle has a protrusion on an outer surface of the conductive portion.
According to a specific aspect of the conductive particle according to the present invention, the conductive particle has an insulating substance provided on an outer surface of the conductive portion.
According to a broad aspect of the present invention, there is provided a conductive material comprising the conductive particles and a binder resin.
According to a specific aspect of the conductive material according to the present invention, the conductive material contains a plurality of the conductive particles, and when a region 1/2 of the particle diameter of the base particles from the outer surface of the base particles toward the center thereof is defined as a region R1, the proportion of the number of conductive particles having the conductive metal present in the region R1 of the base particles is 50% or more, based on 100% of the total number of the conductive particles.
According to a specific aspect of the conductive material according to the present invention, the conductive material contains a plurality of the conductive particles, and when a region of 1/2 distance from the center of the base material particles to the particle diameter of the base material particles on the outer surface thereof is defined as a region R2, the proportion of the number of conductive particles having the conductive metal present in the region R2 of the base material particles is 5% or more, based on 100% of the total number of the conductive particles.
According to a broad aspect of the present invention, there is provided a connection structure comprising: a first member to be connected having a first electrode on a surface, a second member to be connected having a second electrode on a surface, and a connecting portion connecting the first member to be connected and the second member to be connected, wherein the material of the connecting portion is the conductive particles according to any one of claims 1 to 11 or a conductive material containing the conductive particles and a binder resin, and the first electrode and the second electrode are electrically connected by the conductive particles.
ADVANTAGEOUS EFFECTS OF INVENTION
The conductive particles according to the present invention comprise: base particles, and conductive portions disposed on the surfaces of the base particles. In the conductive particles according to the present invention, the base particles contain a conductive metal in the base particles. In the conductive particles according to the present invention, since the conductive particles have the above-described structure, the connection resistance between the electrodes can be effectively reduced, and aggregation between the conductive particles can be effectively suppressed.
Drawings
Fig. 1 is a cross-sectional view showing conductive particles according to a first embodiment of the present invention.
Fig. 2 is a cross-sectional view showing conductive particles according to a second embodiment of the present invention.
Fig. 3 is a cross-sectional view showing conductive particles according to a third embodiment of the present invention.
Fig. 4 is an interface diagram illustrating each region for confirming the presence or absence of conductive metal in the base material particles.
Fig. 5 is a front cross-sectional view schematically showing a connection structure using conductive particles according to the first embodiment of the present invention.
Detailed Description
The following describes the details of the present invention.
(Conductive particles)
The conductive particles according to the present invention include a base particle and a conductive portion disposed on a surface of the base particle. In the conductive particles according to the present invention, the base particles contain a conductive metal in the base particles.
In the conductive particles according to the present invention, since the conductive particles have the above-described structure, the connection resistance between the electrodes can be effectively reduced, and aggregation between the conductive particles can be effectively suppressed.
When a connection structure is produced by connecting electrodes using conductive particles having a small particle diameter, the thickness of the conductive portion in the conductive particles may be increased in order to sufficiently reduce the connection resistance between the electrodes in the vertical direction. However, if the thickness of the conductive portion is increased, a coagulation phenomenon may occur between conductive particles when the conductive portion is formed by plating. If the conductive particles are aggregated, the electrodes adjacent to each other in the lateral direction tend to be connected to each other, and it is often difficult to improve the insulation reliability between the electrodes adjacent to each other in the lateral direction.
Further, if the conductive portions are thinned to suppress aggregation of the conductive particles, aggregation of the conductive particles can be suppressed when the conductive portions are formed by plating, but it is difficult to sufficiently reduce the connection resistance between the electrodes in the up-down direction. In the conventional conductive particles, it is difficult to reduce the connection resistance between electrodes and to suppress aggregation between conductive particles.
The present inventors have found that the use of specific conductive particles can reduce the connection resistance between electrodes and inhibit aggregation of conductive particles. In the present invention, by compressing the conductive particles when the electrodes in the vertical direction are connected, not only the conductive paths can be formed on the surfaces (conductive portions) of the conductive particles, but also the conductive paths can be formed inside the conductive particles (conductive metals). In addition, even if the conductive metal in the conductive particles does not form a complete conductive path, at least the effect of reducing the connection resistance can be achieved. As a result, even when the thickness of the conductive portion is small, the connection resistance between the electrodes in the up-down direction can be sufficiently reduced. Further, since the thickness of the conductive portion is small, aggregation of conductive particles can be suppressed, and the insulation reliability between laterally adjacent electrodes where connection is not desired can be effectively improved. In the present invention, since the above-described structure is provided, the connection resistance between the electrodes can be effectively reduced, and aggregation of the conductive particles can be effectively suppressed. In the present invention, a conductive path (conductive portion) is formed not only on the surface of the base material particle but also in the interior of the base material particle, and the conductive path (conductive portion) can extend into the interior of the base material particle. As a result, the adhesion of the conductive portion in the conductive particle can be effectively improved, and the conductive portion in the conductive particle can be effectively prevented from peeling.
In the present invention, the use of specific conductive particles plays a great role in order to obtain the above-described effects.
The 10% K value (compression elastic modulus when compressed by 10%) of the conductive particles is preferably 100N/mm 2 or more, more preferably 1000N/mm 2 or more, and preferably 25000N/mm 2 or less, more preferably 20000N/mm 2 or less. When the 10% k value of the conductive particles is not less than the lower limit and not more than the upper limit, the connection resistance between the electrodes can be further effectively reduced, cracking of the conductive particles can be further effectively suppressed, and the connection reliability between the electrodes can be further effectively improved.
The conductive particles preferably have a 30% K value (compression elastic modulus at 30% compression) of 100N/mm 2 or more, more preferably 1000N/mm 2 or more, and preferably 15000N/mm 2 or less, more preferably 10000N/mm 2 or less. When the 30% k value of the conductive particles is not less than the lower limit and not more than the upper limit, the connection resistance between the electrodes can be further effectively reduced, cracking of the conductive particles can be further effectively suppressed, and the connection reliability between the electrodes can be further effectively improved.
The ratio of the 10% k value of the conductive particles to the 30% k value of the conductive particles (10% k value of the conductive particles/30% k value of the conductive particles) is preferably 1.5 or more, more preferably 1.55 or more, and preferably 5 or less, more preferably 4.5 or less. When the ratio (10% k value of the conductive particles/30% k value of the conductive particles) is not less than the lower limit and not more than the upper limit, the connection resistance between the electrodes can be further effectively reduced, cracking of the conductive particles can be further effectively suppressed, and the connection reliability between the electrodes can be further effectively improved.
The 10% k value and the 30% k value of the conductive particles can be measured as follows.
A micro-compression tester was used to compress one conductive particle at 25℃with a compression rate of 0.3 mN/sec and a maximum test load of 20mN with a smooth indenter end face of a cylinder (diameter: 100 μm, manufactured by diamond). The load value (N) and the compression displacement (mm) at this time were measured. From the obtained measurement values, the compressive elastic modulus (10% k value and 30% k value) can be obtained by the following expression. As the micro-compression tester, fisher-scope H-100 manufactured by Fisher corporation may be used. The 10% k value and the 30% k value of the conductive particles are preferably calculated by arithmetic average processing of 10% k value and 30% k value of 50 conductive particles arbitrarily selected.
10% K value and 30% K value (N/mm 2)＝(3/21/2)·F·S-3/2·R-1/2
F: load value (N) at 10% or 30% compression deformation of conductive particles
S: compression displacement (mm) when conductive particles are deformed by 10% or 30% by compression
R: radius (mm) of conductive particle
The compressive elastic modulus generally and quantitatively indicates the hardness of the conductive particles. By using the compressive elastic modulus, the hardness of the conductive particles can be quantitatively and uniformly expressed. Meanwhile, the above ratio (10% k value of the conductive particles/30% k value of the conductive particles) can quantitatively and uniformly represent the physical properties of the conductive particles at the time of initial compression.
The particle diameter of the conductive particles is preferably 0.1 μm or more, more preferably 1 μm or more, and preferably 1000 μm or less, more preferably 10 μm or less. When the particle diameter of the conductive particles is not less than the lower limit and not more than the upper limit, the contact area between the conductive particles and the electrode can be sufficiently increased when the electrodes are connected using the conductive particles, and the conductive particles are less likely to form agglomerates when the conductive portion is formed. At the same time, the interval between the electrodes connected via the conductive particles does not become excessively large, and the conductive portions are difficult to peel off from the surfaces of the base particles.
The particle diameter of the conductive particles is preferably an average particle diameter, and preferably a number average particle diameter. The particle size of the conductive particles can be obtained by observing any 50 conductive particles under an electron microscope or an optical microscope, and calculating the average value of the particle sizes of the conductive particles, or by using a particle size distribution measuring apparatus. When observed with an electron microscope or an optical microscope, the average particle diameter of 1 conductive particle was obtained as a particle diameter of a circle equivalent diameter. When observed with an electron microscope or an optical microscope, the average particle diameter of the equivalent diameter of circle of any 50 conductive particles is almost equivalent to the average particle diameter of equivalent diameter of sphere. When the particle size distribution measuring apparatus was used, the average particle size of 1 conductive particle was obtained as the particle size of the sphere equivalent diameter. The average particle diameter of the conductive particles is preferably calculated using a particle size distribution measuring apparatus.
The coefficient of variation (CV value) of the particle diameter of the conductive particles is preferably 10% or less, more preferably 5% or less. When the coefficient of variation in the particle diameter of the conductive particles is equal to or smaller than the upper limit, the conduction reliability and insulation reliability between the electrodes can be further effectively improved.
The coefficient of variation (CV value) can be measured as follows.
CV value (%) = (ρ/Dn) ×100
Ρ: standard deviation of particle diameter of conductive particles
Dn: average particle diameter of conductive particles
The shape of the conductive particles is not limited. The conductive particles may have a spherical shape, a shape other than a spherical shape, a flat shape, or the like.
The present invention will be specifically described below with reference to the accompanying drawings.
Fig. 1 is a cross-sectional view showing conductive particles according to a first embodiment of the present invention.
The conductive particle 1 shown in fig. 1 includes a base particle 2 and a conductive portion 3. The conductive portion 3 is disposed on the surface of the base material particle 2. In the first embodiment, the conductive portion 3 is in contact with the surface of the base material particle 2. The conductive particles 1 are coated particles in which the conductive portions 3 are coated on the surfaces of the base particles 2.
In the conductive particles 1, the conductive portion 3 is a single-layered conductive layer. The conductive particles 1 contain conductive metal in the base particles 2, in the base particles 2. In the conductive particles, the conductive portion may cover the entire surface of the base material particles, or the conductive portion may cover a part of the surface of the base material particles. In the conductive particles, the conductive portion may be a single conductive layer or a multilayer conductive layer composed of two or more layers.
Unlike the conductive particles 11 and 21 described later, the conductive particle 1 does not have a core material. The conductive particles 1 do not have protrusions on the surface. The conductive particles 1 are spherical. The conductive portion 3 has no protrusion on the outer surface. As described above, the conductive particles according to the present invention may have no protrusions on the conductive surface, or may have spherical shapes. The conductive particles 1 do not have an insulating material unlike the conductive particles 11 and 21 described later. However, the conductive particles 1 may have an insulating material disposed on the outer surface of the conductive portion 3.
Fig. 2 is a cross-sectional view showing conductive particles according to a second embodiment of the present invention.
The conductive particles 11 shown in fig. 2 include base particles 2, conductive portions 12, a plurality of core materials 13, and a plurality of insulating materials 14. The conductive portion 12 is disposed on the surface of the base particle 2 so as to be in contact with the base particle 2.
In the conductive particles 11, the conductive portion 12 is a single-layered conductive layer. The conductive particles 11 contain conductive metal in the base particles 2. In the conductive particles, the conductive portion may cover the entire surface of the base material particles, or the conductive portion may cover a part of the surface of the base material particles. In the conductive particles, the conductive portion may be a single conductive layer or a multilayer conductive layer composed of two or more layers.
The conductive particles 11 have a plurality of protrusions 11a on a conductive surface. The conductive portion 12 has a plurality of protrusions 12a on an outer surface. The plurality of core substances 13 are arranged on the surface of the base material particles 2. A plurality of core substances 13 are embedded in the conductive portion 12. The core material 13 is disposed inside the protrusions 11a, 12a. The conductive portion 12 covers the plurality of core materials 13. The outer surface of the conductive portion 12 is raised by the plurality of core materials 13 to form protrusions 11a, 12a.
The conductive particles 11 have an insulating substance 14 disposed on the outer surface of the conductive portion 12. At least a part of the outer surface of the conductive portion 12 is covered with the insulating substance 14. The insulating substance 14 is made of an insulating material, and is an insulating particle. As described above, the conductive particles according to the present invention may have an insulating substance disposed on the outer surface of the conductive portion. However, the conductive particles according to the present invention may not necessarily have an insulating material.
Fig. 3 is a cross-sectional view showing conductive particles according to a third embodiment of the present invention.
The conductive particles 21 shown in fig. 3 include the base particles 2, the conductive portions 22, the plurality of core materials 13, and the plurality of insulating materials 14. The conductive portion 22 as a whole has a first conductive portion 22A on the side of the base material particle 2 and a second conductive portion 22B on the opposite side of the base material particle 2.
The conductive particles 11 and the conductive particles 21 differ only in the conductive portions. That is, the conductive particles 11 are formed with the conductive portions 12 having a single-layer structure, and the conductive particles 21 are formed with the first conductive portions 22A and the second conductive portions 22B having a double-layer structure. The first conductive portion 22A and the second conductive portion 22B are formed as different conductive portions.
The first conductive portion 22A is disposed on the surface of the base material particle 2. The first conductive portion 22A is disposed between the base particle 2 and the second conductive portion 22B. The first conductive portion 22A is in contact with the base particles 2. The second conductive portion 22B is in contact with the first conductive portion 22A. Accordingly, the first conductive portion 22A is disposed on the surface of the base particle 2, and the second conductive portion 22B is disposed on the surface of the first conductive portion 22A. The conductive particles 21 have a plurality of protrusions 21a on the conductive surface thereof. The conductive portion 22 has a plurality of protrusions 22a on its outer surface. The first conductive portion 22A has a plurality of protrusions 22Aa on its outer surface. The second conductive portion 22B has a plurality of protrusions 22Ba on its outer surface.
Hereinafter, other details of the conductive particles will be described.
(Substrate particles)
The material of the base material particles is not particularly limited. The material of the base particles may be an organic material or an inorganic material. Examples of the base particles formed of only the organic material include resin particles. Examples of the base particles formed of only the inorganic material include inorganic particles other than metals. Examples of the base particles formed by the organic material and the inorganic material include organic-inorganic mixed particles. The base material particles are preferably resin particles or organic-inorganic hybrid particles, and more preferably resin particles, from the viewpoint of further optimizing the compression characteristics of the base material particles.
Examples of the organic material include polyolefin resins such as polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinylidene chloride, polyisobutylene, and polybutadiene; acrylic resins such as polymethyl methacrylate and polymethyl acrylate; polycarbonates, polyamides, phenolic resins, melamine formaldehyde resins, benzoguanamine formaldehyde resins, urea formaldehyde resins, phenol resins, melamine resins, benzoguanamine resins, urea resins, epoxy resins, unsaturated polyester resins, saturated polyester resins, polyethylene terephthalate, polysulfones, polyphenylene oxides, polyacetals, polyimides, polyamideimides, polyetheretherketones, polyethersulfones, divinylbenzene polymers, divinylbenzene copolymers, and the like. Examples of the divinylbenzene copolymer include divinylbenzene-styrene copolymer and divinylbenzene- (meth) acrylate copolymer. Since the compression characteristics of the base material particles can be more easily controlled within a preferable range, the material of the base material particles is preferably a polymer obtained by polymerizing one or more polymerizable monomers having an ethylenically unsaturated group.
When the base material particles are obtained by polymerizing a polymerizable monomer having an ethylenically unsaturated group, examples of the polymerizable monomer having an ethylenically unsaturated group include a non-crosslinkable monomer and a crosslinkable monomer.
Examples of the non-crosslinkable monomer include styrene monomers such as styrene, α -methylstyrene and chlorostyrene; vinyl ether compounds such as methyl vinyl ether, ethyl vinyl ether and propyl vinyl ether; acid vinyl ester compounds such as vinyl acetate, vinyl butyrate, vinyl laurate and vinyl stearate; halogen-containing monomers such as vinyl chloride and vinyl fluoride; examples of the (meth) acrylic acid compound include (meth) acrylic acid alkyl ester compounds such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, cetyl (meth) acrylate, stearic (meth) acrylate, cyclohexyl (meth) acrylate, and isobornyl (meth) acrylate; oxygen atom-containing (meth) acrylate compounds such as 2-hydroxyethyl (meth) acrylate, glycerol (meth) acrylate, polyoxyethylene (meth) acrylate, and glycidyl (meth) acrylate; nitrile-containing monomers such as (meth) acrylonitrile; halogen-containing (meth) acrylate compounds such as trifluoromethyl (meth) acrylate and pentafluoroethyl (meth) acrylate; examples of the α -olefin compound include olefin compounds such as diisobutylene, isobutylene, direct olefin, ethylene and propylene; examples of the conjugated diene compound include isoprene and butadiene.
Examples of the crosslinkable monomer include vinyl monomers such as divinylbenzene, 1, 4-dienoxybutane, and divinylsulfone; examples of the (meth) acrylate compound include polyfunctional (meth) acrylate compounds such as tetramethylolmethane tetra (meth) acrylate, polytetramethylene glycol di (meth) acrylate, tetramethylolmethane tri (meth) acrylate, tetramethylolmethane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, glycerol tri (meth) acrylate, glycerol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate, and 1, 4-butanediol di (meth) acrylate; examples of the allyl compound include triallyl (iso) cyanurate, triallyl trimellitate, diallyl phthalate, diallyl acrylamide and diallyl ether; as the silane compound, there is used, examples thereof include tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, and isopropyl trimethoxysilane, isobutyl trimethoxysilane, cyclohexyl trimethoxysilane, n-hexyl trimethoxysilane, n-octyl triethoxysilane, n-decyl trimethoxysilane alkoxysilane compounds such as phenyltrimethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diisopropyldimethoxysilane, trimethoxysilylistyrene, gamma- (meth) acryloxypropyltrimethoxysilane, 1, 3-divinyl tetramethyldisiloxane, methylphenyldimethoxysilane, diphenyldimethoxysilane and the like; vinyl trimethoxy silane, vinyl triethoxy silane, dimethoxy methyl vinyl silane dimethoxyethylvinylsilane, diethoxymethylvinylsilane, diethoxyethylvinylsilane ethyl methyl divinyl silane, methyl vinyl dimethoxy silane, ethyl vinyl dimethoxy silane, methyl vinyl diethoxy silane, ethyl vinyl diethoxy silane alkoxysilanes having polymerizable double bonds such as p-styryl trimethoxysilane, 3-methacryloxypropyl methyl dimethoxy silane, 3-methacryloxypropyl trimethoxysilane, 3-methacryloxypropyl methyl diethoxy silane, 3-methacryloxypropyl triethoxy silane, and 3-acryloxypropyl trimethoxysilane; cyclic siloxanes such as decamethyl cyclopentasiloxane; modified (reactive) silicone oils such as single-end modified silicone oils, double-end silicone oils, and side chain type silicone oils; and carboxyl group-containing monomers such as (meth) acrylic acid, maleic acid and maleic anhydride.
The base material particles can be obtained by polymerizing a polymerizable monomer having the ethylenically unsaturated group. The polymerization method is not particularly limited, and known methods such as radical polymerization, ion polymerization, polycondensation (condensation polymerization, polycondensation), addition polymerization, living polymerization, and living radical polymerization can be used. Further, as other polymerization methods, suspension polymerization in the presence of a radical polymerization initiator can be cited.
Examples of the inorganic material include silica, alumina, barium titanate, zirconium oxide, carbon black, silicate glass, borosilicate glass, lead glass, soda lime glass, and aluminosilicate glass.
The base particles may be organic-inorganic mixed particles. The substrate particles may be core-shell particles. When the base particles are organic-inorganic mixed particles, examples of the inorganic substance as a material of the base particles include silica, alumina, barium titanate, zirconium oxide, carbon black, and the like. The inorganic substance is preferably a nonmetal. The substrate particles formed of silica are not particularly limited, and examples thereof include: the substrate particles obtained by hydrolyzing a silicon compound having two or more hydrolyzable alkoxysilyl groups to form crosslinked polymer particles and then firing the particles as needed. Examples of the organic-inorganic hybrid particles include organic-inorganic hybrid particles formed of a crosslinked alkoxysilyl polymer and an acrylic resin.
The organic-inorganic hybrid particles are preferably core-shell organic-inorganic hybrid particles having a core and a shell disposed on the surface of the core. The core is preferably an organic core. The shell is preferably an inorganic shell. The base particles are preferably organic-inorganic hybrid particles having an organic core and an inorganic shell disposed on the surface of the organic core.
The material of the organic core may be the organic material described above.
The inorganic shell material may be the inorganic material mentioned above as the base particle material. The material of the inorganic shell is preferably silica. The inorganic shell is preferably: an inorganic shell formed by forming a metal alkoxide into a shell on the surface of the core by a sol-gel method and firing the shell. The metal alkoxide is preferably an alkoxysilane. The inorganic shell is preferably formed of an alkoxysilane.
The BET specific surface area of the base particles is preferably 8m 2/g or more, more preferably 12m 2/g or more, and preferably 1200m 2/g or less, more preferably 1000m 2/g or less. When the BET specific surface area is not less than the lower limit and not more than the upper limit, the inside of the base material particles can be further easily contained with a conductive metal. When the BET specific surface area is not less than the lower limit and not more than the upper limit, the connection resistance between the electrodes can be further effectively reduced, and aggregation of the conductive particles can be further effectively suppressed. Meanwhile, if the BET specific surface area is not less than the lower limit and not more than the upper limit, the insulation reliability between the electrodes can be further effectively improved. Further, when the BET specific surface area is not less than the lower limit and not more than the upper limit, adhesion of the conductive portion in the conductive particle can be further effectively improved, and peeling of the conductive portion in the conductive particle can be further effectively suppressed.
The BET specific surface area of the base particles can be measured by the BET method from the adsorption isotherm of nitrogen. Examples of the measurement device for the BET specific surface area of the base particles include "NOVA4200e" manufactured by Cantachrome Instruments.
The total pores Rong Youxuan of the base material particles are 0.01cm 3/g or more, more preferably 0.1cm 3/g or more, and preferably 3cm 3/g or less, more preferably 1.5cm 3/g or less. When the total pore volume is not less than the lower limit and not more than the upper limit, the inside of the base material particles can be further easily contained with a conductive metal. When the total pore volume is not less than the lower limit and not more than the upper limit, the connection resistance between the electrodes can be further effectively reduced, and aggregation of the conductive particles can be further effectively suppressed. Meanwhile, if the total pore volume is not less than the lower limit and not more than the upper limit, the insulation reliability between the electrodes can be further effectively improved. Further, if the total pore volume is not less than the lower limit and not more than the upper limit, adhesion of the conductive portion in the conductive particle can be further effectively improved, and peeling of the conductive portion in the conductive particle can be further effectively suppressed.
The total pore volume of the substrate particles can be measured by the BJH method from the adsorption isotherm of nitrogen. Examples of the measurement device for the total pore volume of the base particles include "NOVA4200e" manufactured by Cantachrome Instruments.
The average pore diameter of the base particles is preferably 10nm or less, more preferably 5nm or less. The lower limit of the average pore diameter of the base particles is not particularly limited. The average pore diameter of the base particles may be 1nm or more. When the average pore diameter of the base material particles is not less than the lower limit and not more than the upper limit, the inside of the base material particles can be further easily contained with a conductive metal. When the average pore diameter is not less than the lower limit and not more than the upper limit, the connection resistance between the electrodes can be further effectively reduced, and aggregation of the conductive particles can be further effectively suppressed. Further, if the average pore diameter is not less than the lower limit and not more than the upper limit, the insulation reliability between the electrodes can be further effectively improved. Further, when the average pore diameter is not less than the lower limit and not more than the upper limit, adhesion of the conductive portion in the conductive particle can be further effectively improved, and peeling of the conductive portion in the conductive particle can be further effectively suppressed.
The average pore diameter of the substrate particles can be measured by the BJH method from adsorption isotherms of nitrogen. Examples of the device for measuring the average pore diameter of the base particles include "NOVA4200e" manufactured by Cantachrome Instruments.
The porosity of the base material particles is preferably 5% or more, more preferably 10% or more, and preferably 90% or less, more preferably 70% or less. If the porosity is not less than the lower limit and not more than the upper limit, the inside of the base material particles can be further easily contained with a conductive metal. When the porosity is not less than the lower limit and not more than the upper limit, the connection resistance between the electrodes can be further effectively reduced, and aggregation of the conductive particles can be further effectively suppressed. Further, if the porosity is not less than the lower limit and not more than the upper limit, the insulation reliability between the electrodes can be further effectively improved. Further, if the porosity is not less than the lower limit and not more than the upper limit, adhesion of the conductive portion in the conductive particle can be further effectively improved, and peeling of the conductive portion in the conductive particle can be further effectively suppressed.
The porosity of the substrate particles can be calculated by measuring the cumulative penetration amount of mercury relative to the pressure applied by mercury porosimetry. Examples of the device for measuring the porosity of the base material particles include "Poremaster" manufactured by Cantachrome Instruments.
For example, the substrate particles satisfying the preferable ranges of the BET specific surface area, the porosity, and the like can be obtained by a method for producing substrate particles having the following steps. That is, a step of mixing a polymerizable monomer and an organic solvent that does not react with the polymerizable monomer to prepare a polymerizable monomer solution. And a step of adding the polymerizable monomer solution and the anionic dispersion stabilizer to a polar solvent and emulsifying the mixture to obtain an emulsion. And a step of adding the emulsion in a small amount to allow the seed particles to absorb the monomer, thereby obtaining a suspension containing the seed particles swollen with the monomer. And polymerizing the polymerizable monomer to obtain base material particles. Examples of the polymerizable monomer include monofunctional monomers and polyfunctional monomers. The organic solvent that does not react with the polymerizable monomer is not particularly limited as long as it is a material that is not compatible with a polar solvent such as water that is a solvent of the polymerization system. Examples of the organic solvent include cyclohexane, toluene, xylene, ethyl acetate, butyl acetate, allyl acetate, propyl acetate, chloroform, methylcyclohexane, and methyl ethyl ketone. The amount of the organic solvent to be added is preferably 105 to 215 parts by weight, more preferably 110 to 210 parts by weight, based on 100 parts by weight of the polymerizable monomer component. When the amount of the organic solvent to be added is within the above-mentioned preferred range, the BET specific surface area, the porosity and the like can be controlled within a further preferred range, and thus dense fine pores can be more easily obtained in the interior of the particles.
Since the substrate particles satisfying the preferable ranges of the BET specific surface area, the porosity, and the like have many pores in the substrate particles, when the conductive portions are formed on the surfaces of the substrate particles, the conductive portions enter the fine voids in the substrate particles, and the conductive metal can be easily contained in the substrate particles. In addition, among the conductive particles, it is preferable that the conductive particles are compressed when electrodes in the vertical direction are connected, so that conductive metals in the base particles are brought into contact with each other to form conductive paths. In the conductive particles, not only conductive paths are formed on the surfaces (conductive portions) of the conductive particles, but also conductive paths are formed in the interiors (conductive metals) of the conductive particles. As a result, even when the thickness of the conductive portion is small, the connection resistance between the electrodes in the up-down direction can be sufficiently reduced. Further, since the thickness of the conductive portion is small, aggregation of conductive particles can be suppressed, and insulation reliability between laterally adjacent electrodes which cannot be connected can be effectively improved. In addition, in the above conductive particles, when the conductive portions are formed on the surfaces of the base particles, the conductive portions extend into the fine voids inside the base particles, so that the adhesion of the conductive portions in the conductive particles can be effectively improved, and the conductive portions in the conductive particles can be effectively prevented from peeling.
The particle diameter of the base material particles is preferably 0.1 μm or more, more preferably 1 μm or more. The particle diameter of the base particles is preferably 1000 μm or less, more preferably 500 μm or less, still more preferably 300 μm or less, still more preferably 50 μm or less, still more preferably 10 μm or less. When the particle diameter of the base material particles is equal to or larger than the lower limit, the contact area between the conductive particles and the electrodes becomes larger, the conduction reliability between the electrodes can be further improved, and the connection resistance between the electrodes connected via the conductive particles can be further reduced. In addition, the conductive particles can be formed on the surface of the base material particles by electroless plating, so that aggregation of the conductive particles is less likely to occur. When the particle diameter of the base material particles is equal to or less than the upper limit, the conductive particles are easily compressed sufficiently, and the connection resistance between the electrodes can be further reduced, and the interval between the electrodes can be further reduced.
The particle diameter of the base material particles is particularly preferably 1 μm or more and 3 μm or less. When the particle diameter of the base material particles is in the range of 1 μm or more and 3 μm or less, aggregation is less likely to occur when forming conductive portions on the surfaces of the base material particles, and aggregated conductive particles are less likely to be formed.
The particle diameter of the base material particles represents a number average particle diameter. The particle size of the base material particles can be determined by observing any 50 base material particles under an electron microscope or an optical microscope and calculating the average value of the particle sizes of the base material particles, or by using a particle size distribution measuring apparatus. When observed with an electron microscope or an optical microscope, the average particle diameter of 1 substrate particle was obtained as a particle diameter of a circle equivalent diameter. When observed using an electron microscope or an optical microscope, the average particle diameter of the equivalent diameter of the sphere of any 50 base particles was almost equivalent to the average particle diameter of the equivalent diameter of the sphere. When the particle size distribution measuring apparatus was used, the average particle size of 1 substrate particle was obtained as the particle size of the sphere equivalent diameter. The average particle diameter of the base particles is preferably calculated using a particle size distribution measuring apparatus. In the conductive particles, the particle diameter of the base particles may be measured, for example, as follows.
The conductive particles were added to "Technobit4000" manufactured by Kulzer company and dispersed so that the content of the conductive particles was 30 wt%, to prepare an embedding resin for conductive particle inspection. An ion milling apparatus (IM 4000 manufactured by hitachi high technology corporation) was used to cut a cross section of the conductive particles so as to pass through the vicinity of the center of the conductive particles dispersed in the embedding resin for inspection. Subsequently, using a field emission scanning electron microscope (FE-SEM), the image magnification was set to 25000 times, 50 conductive particles were randomly selected, and the base particles of each conductive particle were observed. The particle diameters of the base particles in the respective conductive particles were measured, and arithmetic average treatment was performed thereon to obtain the particle diameters of the base particles.
(Conductive portion and conductive Metal)
The conductive particles according to the present invention include a base particle and a conductive portion disposed on a surface of the base particle. In the conductive particles according to the present invention, the base particles contain a conductive metal in the base particles. The conductive portion preferably contains a metal. The metal constituting the conductive portion is not limited. The conductive metal is not limited. The metal constituting the conductive portion and the conductive metal may be the same metal or may be different metals. Preferably, the metal having the largest content in the conductive portion and the metal having the largest content in the conductive metal are the same metal.
Examples of the metal constituting the conductive portion and the conductive metal include gold, silver, palladium, copper, platinum, zinc, iron, tin, lead, aluminum, cobalt, indium, nickel, chromium, titanium, antimony, bismuth, thallium, germanium, cadmium, silicon, tungsten, molybdenum, and alloys thereof. The metal constituting the conductive portion and the conductive metal include tin-doped indium oxide (ITO) and solder. The metal constituting the conductive portion and the conductive metal may be used singly or in combination.
The conductive portion preferably contains nickel, gold, palladium, silver, or copper, more preferably nickel, gold, or palladium, from the viewpoint of further effectively reducing the connection resistance between the electrodes.
The nickel content in 100 wt% of the nickel-containing conductive portion is preferably 10 wt% or more, more preferably 50 wt% or more, still more preferably 60 wt% or more, still more preferably 70 wt% or more, and particularly preferably 90 wt% or more. The nickel content in 100 wt% of the nickel-containing conductive portion may be 97 wt% or more, 97.5 wt% or more, or 98 wt% or more.
It is to be noted that, due to oxidation, hydroxyl groups are often present on the surface of the conductive portion. In general, hydroxyl groups are present on the surface of the conductive portion formed of nickel due to oxidation. An insulating material can be disposed on the surface of the conductive portion having a hydroxyl group (the surface of the conductive particle) through a chemical bond.
The conductive portion may be formed of one layer. The conductive portion may be formed of a plurality of layers. That is, the conductive portion may have a laminated structure of two or more layers. If the conductive portion is formed of a plurality of layers, the metal constituting the outermost layer is preferably an alloy containing gold, nickel, palladium, copper or tin, and silver, and more preferably gold. If the metal constituting the outermost layer is the above-mentioned preferable metal, the connection resistance between the electrodes is further reduced. Further, if the metal constituting the outermost layer is gold, the corrosion resistance is further improved.
There is no particular limitation on the method of forming the conductive portion on the surface of the base material particle. Examples of the method for forming the conductive portion include electroless plating, electroplating, physical collision, mechanochemical reaction, physical vapor deposition or physical adsorption, and a method of applying a paste containing a metal powder or a metal powder and an adhesive to the surface of the base material particles. The method of forming the conductive portion is preferably electroless plating, electroplating, or physical impact. Examples of the physical vapor deposition method include vacuum vapor deposition, ion plating, and ion sputtering. As a method of the physical collision, sheeter Composer (manufactured by the trade company, schlem) or the like can be used.
The method for incorporating the conductive metal into the base material particles is not particularly limited. Examples of the method for containing the conductive metal in the substrate particles include a method for electroless plating using the substrate particles (substrate particle bodies) as porous particles and a method for electroplating using the substrate particles (substrate particle bodies) as porous particles. Since many pores exist in the interior of the base material particles (base material particle body) as the porous particles, the conductive portion forming material (plating solution or the like) can be immersed in the fine pores in the interior of the base material particles when forming the conductive portion on the surface of the base material particles. By precipitating the conductive metal from the conductive portion forming material penetrating into the interior of the base material particles, the interior of the base material particles can be easily filled with the conductive metal. Examples of the base particles as porous particles include those satisfying the preferable ranges of the BET specific surface area, the porosity, and the like.
The thickness of the conductive portion is preferably 0.005 μm or more, more preferably 0.01 μm or more, and preferably 10 μm or less, more preferably 1 μm or less, and further preferably 0.3 μm or less. If the conductive portion has a multilayer structure, the thickness of the conductive portion refers to the thickness of the entire conductive portion. When the thickness of the conductive portion is not less than the lower limit and not more than the upper limit, sufficient conductivity can be obtained, and the conductive particles can be sufficiently deformed when the electrodes are connected without becoming too hard.
If the conductive portion is formed of a plurality of layers, the thickness of the conductive portion of the outermost layer is preferably 0.001 μm or more, more preferably 0.01 μm or more, and preferably 0.5 μm or less, more preferably 0.1 μm or less. When the thickness of the outermost conductive portion is not less than the lower limit and not more than the upper limit, the coating by the outermost conductive portion can be made uniform, the corrosion resistance can be sufficiently improved, and the connection resistance between the electrodes can be sufficiently reduced. Further, if the metal constituting the outermost layer is gold, the thinner the thickness of the outermost layer is, the more cost can be reduced.
For example, the thickness of the conductive portion can be measured by observing a cross section of the conductive particle using a Transmission Electron Microscope (TEM). The thickness of the conductive portion is preferably calculated as an average value of the thicknesses of five positions of any conductive portion, and more preferably calculated as an average value of the thicknesses of one conductive portion of one conductive particle. The thickness of the conductive portion is preferably obtained by calculating an average value of the thicknesses of the conductive portions of the conductive particles for any 10 conductive particles.
The content of the conductive metal in 100% by volume of the conductive particles is preferably 5% by volume or more, more preferably 10% by volume or more, and preferably 70% by volume or less, more preferably 50% by volume or less. When the content of the conductive metal is not less than the lower limit and not more than the upper limit, the connection resistance between the electrodes can be further effectively reduced, and aggregation of the conductive particles can be further effectively suppressed. Further, if the content of the conductive metal is not less than the lower limit and not more than the upper limit, the insulation reliability between the electrodes can be further effectively improved. Further, when the content of the conductive metal is not less than the lower limit and not more than the upper limit, adhesion of the conductive portion in the conductive particle can be further effectively improved, and peeling of the conductive portion in the conductive particle can be further effectively suppressed. The content of the conductive metal in 100% by volume of the conductive particles is preferably 5% by volume or more, more preferably 10% by volume or more, and preferably 50% by volume or less, more preferably 40% by volume or less, from the viewpoint of further optimizing the compression characteristics of the conductive particles. The content of the conductive metal in 100% by volume of the conductive particles is preferably 10% by volume or more, more preferably 20% by volume or more, and preferably 50% by volume or less, more preferably 40% by volume or less, from the viewpoint of further effectively reducing the connection resistance between the electrodes. The content of the conductive metal is particularly preferably 10% by volume or more and 40% by volume or less in 100% by volume of the conductive particles. When the content of the conductive metal is in the range of 10% by volume or more and 40% by volume or less, both optimization of compression characteristics of the conductive particles and reduction of connection resistance between electrodes can be achieved at a higher level. The content of the conductive metal is the total content of the metal constituting the conductive portion and the conductive metal contained in the base material particles. As to whether or not the conductive metal is contained in the base material particles, it is preferable to determine the first ratio and the second ratio, which will be described later.
The content of the above-mentioned conductive metal can be calculated according to the following formula.
Content of conductive metal (volume%) =d×m/Dmetal ×100
D: specific gravity of conductive particles
M: metallization ratio of conductive particles
Dmetal: specific gravity of conductive metal
The metallization ratio of the conductive particles may be calculated using ICP emission spectrometry or the like, and the specific gravity of the conductive particles may be measured using a true gravimeter or the like. Further, the specific gravity of the conductive metal can be calculated using the value inherent to the metal. The metallization ratio of the conductive particles means the content (g) of the conductive metal contained in the conductive particles 1g expressed in terms of a ratio, that is, the content (g) of the conductive metal contained in the conductive particles 1 g/the conductive particles 1g.
The content of the conductive metal contained in the base particles is preferably 0.1% by volume or more, more preferably 1% by volume or more, and preferably 30% by volume or less, more preferably 20% by volume or less, of 100% by volume of the conductive particles. When the content of the conductive metal is not less than the lower limit and not more than the upper limit, the connection resistance between the electrodes can be further effectively reduced, and aggregation of the conductive particles can be further effectively suppressed. Further, when the content of the conductive metal is not less than the lower limit and not more than the upper limit, adhesion of the conductive portion in the conductive particle can be further effectively improved, and peeling of the conductive portion in the conductive particle can be further effectively suppressed.
From the viewpoint of further optimizing the compression characteristics of the conductive particles, the content of the conductive metal contained in the conductive portion is preferably 0.1% by volume or more, more preferably 1% by volume or more, and preferably 30% by volume or less, more preferably 20% by volume or less, of 100% by volume of the conductive particles. In terms of further effectively reducing the connection resistance between the electrodes, the content of the conductive metal contained in the conductive portion is preferably 0.1% by volume or more, more preferably 1% by volume or more, and preferably 30% by volume or less, more preferably 20% by volume or less, of 100% by volume of the conductive particles.
(Core substance)
The conductive particles preferably have protrusions on the outer surface of the conductive portion. The conductive particles preferably have protrusions on the conductive surface. The number of the protrusions is preferably plural. An oxide film is often formed on the surface of the electrode connected by the conductive particles. If conductive particles having protrusions on the surface of the conductive portion are used, the oxide film can be effectively removed by the protrusions by disposing and pressing the conductive particles between the electrodes. Therefore, the electrode and the conductive portion are reliably contacted with each other, and the connection resistance between the electrodes is further reduced. Further, if the conductive particles are provided with an insulating substance or the conductive particles are dispersed in a binder resin to be used as a conductive material, the insulating substance or the binder resin between the conductive particles and the electrode can be more effectively eliminated by the protrusions of the conductive wire particles. Therefore, the connection resistance between the electrodes can be further reduced.
If the core material is formed of a metal and the core material exists in the conductive portion, the core material may be regarded as a part of the conductive portion.
As a method of forming the above-mentioned protrusion, there may be mentioned: a method of forming a conductive portion by electroless plating after attaching a core substance to the surface of a base particle, a method of forming a conductive portion by electroless plating, and the like. In addition, the core material may not be used in order to form the protrusions.
As another method for forming the above-mentioned protrusion, there may be mentioned: and a method of adding a core material at a stage in the middle of forming a conductive portion on the surface of a base material particle. In addition, in order to form the protrusions, a method may be used in which the conductive portion is formed on the base material particles by electroless plating without using the core material, and then the plating material is deposited in a protruding form on the surface of the conductive portion, and further the conductive portion is formed by electroless plating.
As a method for attaching the core substance to the surface of the base material particle, there can be mentioned: a method of adding a core substance to a dispersion of base particles and accumulating and adhering the core substance to the surface of the base particles by van der Waals force, a method of adding a core substance to a container containing the base particles and adhering the core substance to the surface of the base particles by a mechanical action such as a rotary container, and the like. From the viewpoint of controlling the amount of the core material to be adhered, the method of adhering the core material to the surface of the base material particles is preferably a method of accumulating and adhering the core material to the surface of the base material particles in the dispersion.
Examples of the substance constituting the core substance include a conductive substance and a nonconductive substance. Examples of the conductive material include metals, metal oxides, conductive nonmetallic materials such as graphite, and conductive polymers. The conductive polymer may be polyacetylene or the like. Examples of the nonconductive material include silica, alumina, and zirconia. From the viewpoint of further effectively removing the oxide film, the core material is preferably hard. The core material is preferably a metal from the viewpoint of further effectively reducing the connection resistance between the electrodes.
The above metal is not particularly limited. The metals mentioned above may be: metals such as gold, silver, copper, platinum, zinc, iron, lead, tin, aluminum, zirconium, indium, nickel, chromium, titanium, antimony, bismuth, germanium, and cadmium, and alloys composed of two or more metals such as tin-lead alloy, tin-copper alloy, tin-silver alloy, tin-lead-silver alloy, and tungsten carbide. The metal is preferably nickel, copper, silver or gold from the viewpoint of further effectively reducing the connection resistance between the electrodes. The metal may be the same as or different from the metal constituting the conductive portion (conductive layer).
The shape of the core material is not limited. The core material is preferably in the shape of a block. Examples of the core material include a particulate block, an aggregated block formed by aggregating a plurality of fine particles, and an amorphous block.
The particle diameter of the core material is preferably 0.001 μm or more, more preferably 0.05 μm or more, and preferably 0.9 μm or less, more preferably 0.2 μm or less. If the particle diameter of the core material is not less than the lower limit and not more than the upper limit, the connection resistance between the electrodes can be further effectively reduced.
The particle diameter of the core material is preferably an average particle diameter, and more preferably a number average particle diameter. The particle diameter of the core material can be determined, for example, by observing any 50 core materials under an electron microscope or an optical microscope and calculating an average value of particle diameters of the respective core materials, or by using a particle size distribution measuring apparatus. When observed with an electron microscope or an optical microscope, the average particle diameter of 1 core material was obtained as a particle diameter of a circle equivalent diameter. The average particle diameter of the equivalent diameter of the sphere of any 50 core materials is almost equivalent to the average particle diameter of the equivalent diameter of the sphere when observed using an electron microscope or an optical microscope. When the particle size distribution measuring apparatus was used, the average particle size of 1 core material was obtained as the particle size of the sphere equivalent diameter. The average particle diameter of the core material is preferably calculated using a particle size distribution measuring apparatus.
The number of protrusions of the conductive particles is preferably 3 or more, more preferably 5 or more, on average 1. The upper limit of the number of the above-mentioned protrusions is not particularly limited. The upper limit of the number of the protrusions may be appropriately selected in consideration of the particle diameter of the conductive particles and the like. If the number of the protrusions is equal to or greater than the lower limit, the connection resistance between the electrodes can be further effectively reduced.
The number of the protrusions can be obtained by observing any conductive particles under an electron microscope or an optical microscope. The number of protrusions is preferably obtained by observing any 50 conductive particles under an electron microscope or an optical microscope and calculating an average value of the number of protrusions of each conductive particle.
The height of the protrusions is preferably 0.001 μm or more, more preferably 0.05 μm or more, and preferably 0.9 μm or less, more preferably 0.2 μm or less. If the height of the protrusions is not less than the lower limit and not more than the upper limit, the connection resistance between the electrodes can be further effectively reduced.
The height of the protrusions can be obtained by observing the protrusions in any conductive particle under an electron microscope or an optical microscope. The height of the protrusions is preferably calculated as the average value of the heights of all protrusions of an average of 1 conductive particle. The height of the protrusions is preferably obtained by calculating the average value of the heights of the protrusions of each conductive particle for any 50 conductive particles.
(Insulating substance)
The conductive particles preferably include an insulating material disposed on an outer surface of the conductive portion. In this case, when the conductive particles are used for connection between electrodes, short-circuiting between adjacent electrodes can be prevented more effectively. Specifically, when a plurality of conductive particles are in contact with each other, since an insulating substance is present between a plurality of electrodes, it is possible to prevent a short circuit between adjacent electrodes in the lateral direction rather than the up-down direction. When the electrodes are connected, the conductive particles are pressurized by using the two electrodes, so that the insulating material between the conductive portions of the conductive particles and the electrodes can be easily removed. Further, if the conductive particles have protrusions on the outer surface of the conductive portion, the insulating substance between the conductive portion of the conductive particles and the electrode can be more easily removed.
The insulating material is preferably insulating particles in view of further facilitating the removal of the insulating material when the electrodes can be pressed together.
Examples of the material of the insulating substance include the organic material, the inorganic material, and the inorganic material as the material of the base particles. The material of the insulating substance is preferably the organic material.
Examples of the other material of the insulating material include a polyolefin compound, (meth) acrylate polymer, (meth) acrylate copolymer, block polymer, thermoplastic resin, crosslinked product of thermoplastic resin, thermosetting resin, and water-soluble resin. The insulating material may be used alone or in combination of two or more.
Examples of the polyolefin compound include polyethylene, ethylene-vinyl acetate copolymer, and ethylene-acrylic acid ester copolymer. Examples of the (meth) acrylate polymer include polymethyl (meth) acrylate, polydodecyl (meth) acrylate, and poly (meth) acrylic stearate. Examples of the block polymer include polystyrene, styrene-acrylate copolymer, SB-type styrene-butadiene block copolymer, SBS-type styrene-butadiene block copolymer, hydrogenated products thereof, and the like. Examples of the thermoplastic resin include vinyl polymers and vinyl copolymers. Examples of the thermosetting resin include epoxy resins, phenolic resins, and melamine resins. Examples of the crosslinked product of the thermoplastic resin include polyethylene glycol methacrylate, alkoxylated trimethylolpropane methacrylate, and alkoxylated pentaerythritol methacrylate. Examples of the water-soluble resin include polyvinyl alcohol, polyacrylic acid, polyacrylamide, polyvinylpyrrolidone, polyethylene oxide, and methylcellulose. In addition, a chain transfer agent may be used to adjust the degree of polymerization. Examples of the chain transfer agent include mercaptans and carbon tetrachloride.
Examples of the method for disposing the insulating material on the surface of the conductive portion include a chemical method, a physical method, a mechanical method, and the like. Examples of the chemical method include an interfacial polymerization method, a suspension polymerization method in the presence of particles, and an emulsion polymerization method. Examples of the physical method or the mechanical method include a spray drying method, a hybrid method, an electrostatic adsorption method, a spray method, a dipping method, and a vacuum deposition method. In the case where the electrodes are electrically connected, the method of disposing the insulating material on the surface of the conductive portion is preferably a physical method from the viewpoint of further effectively improving insulation reliability and conduction reliability.
The outer surfaces of the conductive portions and the outer surfaces of the insulating material may be covered with a compound having a reactive functional group. The outer surface of the conductive portion and the outer surface of the insulating material may not be directly chemically bonded, but may be indirectly chemically bonded through a compound having a reactive functional group. After introducing a carboxyl group into the outer surface of the conductive portion, the carboxyl group may be chemically bonded to a functional group on the outer surface of the insulating material through a polyelectrolyte such as polyethyleneimine.
If the insulating material is an insulating particle, the particle diameter of the insulating particle may be appropriately selected according to the particle diameter of the conductive particle, the use of the conductive particle, and the like. The particle diameter of the insulating particles is preferably 10nm or more, more preferably 100nm or more, further preferably 300nm or more, particularly preferably 500nm or more, and preferably 4000nm or less, more preferably 2000nm or less, further preferably 1500nm or less, particularly preferably 1000nm or less. When the particle diameter of the insulating particles is not less than the lower limit, the conductive portions of the plurality of conductive particles are not likely to contact each other when the conductive particles are dispersed in the binder resin. When the particle diameter of the insulating particles is equal to or smaller than the upper limit, it is not necessary to excessively raise the pressure to exclude the insulating particles between the electrodes and the conductive particles when connecting the electrodes, and it is also unnecessary to perform high-temperature heating.
The particle diameter of the insulating particles is preferably an average particle diameter, and more preferably a number average particle diameter. The particle size of the insulating particles can be determined by, for example, observing any 50 insulating particles under an electron microscope or an optical microscope, and calculating the average value of the particle sizes of the respective insulating particles, or by using a particle size distribution measuring apparatus. When observed with an electron microscope or an optical microscope, the average particle diameter of 1 insulating particle was obtained as a diameter of a circle equivalent diameter. When observed with an electron microscope or an optical microscope, the average particle diameter of the equivalent diameter of round of any 50 insulating particles was almost equivalent to the average particle diameter of equivalent diameter of sphere. When the particle size distribution measuring apparatus was used, the average particle size of 1 insulating particle was obtained as the particle size of the sphere equivalent diameter. The average particle diameter of the insulating particles is preferably calculated using a particle size distribution measuring apparatus. In the conductive particles, the particle diameter of the insulating particles can be measured, for example, as follows.
The electroconductive particles were added to "Technobit4000,4000" manufactured by Kulzer corporation and dispersed so that the content of the electroconductive particles was 30 wt%, to prepare an electroconductive particle inspection embedded resin. An ion milling apparatus (IM 4000 manufactured by hitachi high technology corporation) was used to cut a cross section of the conductive particles so as to pass through the vicinity of the center of the conductive particles dispersed in the embedding resin for inspection. Subsequently, 50 conductive particles were randomly selected and the insulating particles of each conductive particle were observed using a field emission scanning electron microscope (FE-SEM) with an image magnification set to 5 ten thousand times. The particle diameter of the insulating particles in each conductive particle was measured, and arithmetic average treatment was performed thereon to obtain the particle diameter of the insulating particles.
The ratio of the particle diameter of the conductive particles to the particle diameter of the insulating particles (particle diameter of the conductive particles/particle diameter of the insulating particles) is preferably 4 or more, more preferably 8 or more, and preferably 200 or less, more preferably 100 or less. When the ratio (particle diameter of the conductive particles/particle diameter of the insulating particles) is equal to or greater than the lower limit and equal to or less than the upper limit, insulation reliability and conduction reliability can be further effectively improved when the electrodes are electrically connected.
(Conductive Material)
The conductive material according to the present invention contains the conductive particles and the binder resin. The conductive particles are preferably dispersed in an adhesive resin, and are preferably dispersed in an adhesive resin to be used as a conductive material. The conductive material is preferably an anisotropic conductive material. The above-mentioned conductive material is preferably used for electrical connection between the electrodes. The conductive material is preferably a conductive material for a connection line. In the above-described conductive material, since the above-described conductive particles are used, the connection resistance between the electrodes can be further effectively reduced, and aggregation between the conductive particles can be further effectively suppressed. In the above-described conductive material, the use of the above-described conductive particles can further effectively improve the reliability of insulation between electrodes.
The conductive material preferably contains a plurality of the conductive particles. When the region of 1/2 distance from the outer surface of the base material particle to the particle diameter of the base material particle toward the center thereof is defined as a region R1, the ratio of the number of conductive particles having the conductive metal present in the region R1 of the base material particle (hereinafter, also referred to as a first ratio) is preferably 50% or more, more preferably 60% or more, based on 100% of the total number of conductive particles. The upper limit of the first ratio is not particularly limited. The first ratio may be 100% or less. When the first ratio is equal to or greater than the lower limit, the connection resistance between the electrodes can be further effectively reduced, and aggregation of the conductive particles can be further effectively suppressed. Further, if the first ratio is equal to or greater than the lower limit, the insulation reliability between the electrodes can be further effectively improved. Further, when the first ratio is not less than the lower limit and not more than the upper limit, adhesion of the conductive portion in the conductive particle can be further effectively improved, and peeling of the conductive portion in the conductive particle can be further effectively suppressed. If the first ratio exceeds 0%, it can be determined that the base material particles contain a conductive metal. The region R1 is a region outside the broken line L1 of the base particle 2 in fig. 4. The region R1 is an outer surface portion of the base material particle. The region R1 is a region different from the central portion of the base material particle.
When the region of 1/2 distance from the center of the base material particle to the outer surface of the base material particle is defined as a region R2, the ratio of the number of conductive particles having the conductive metal present in the region R2 of the base material particle (hereinafter, also referred to as a second ratio) is preferably 5% or more, more preferably 10% or more, based on 100% of the total number of conductive particles. The upper limit of the second ratio is not particularly limited. The second ratio may be 100% or less. When the second ratio is equal to or greater than the lower limit, the connection resistance between the electrodes can be further effectively reduced, and aggregation of the conductive particles can be further effectively suppressed. Further, if the second ratio is equal to or greater than the lower limit, the insulation reliability between the electrodes can be further effectively improved. Meanwhile, if the second ratio is not less than the lower limit and not more than the upper limit, adhesion of the conductive portion in the conductive particle can be further effectively improved, and peeling of the conductive portion in the conductive particle can be further effectively suppressed. If the second ratio exceeds 0%, it can be determined that the inside of the base material particles contains the conductive metal. The region R2 is a region further inside than the broken line L1 of the base particle 2 in fig. 4. The region R2 is a central portion of the base material particle. The region R2 is a region different from the outer surface portion of the base material particle.
The first ratio and the second ratio may be calculated as follows.
The conductive particles are recovered from the conductive material by filtration or the like. The conductive particles were added to "Technobit4000,4000" manufactured by Kulzer corporation and dispersed so that the content of the recovered conductive particles was 30 wt%, to prepare an embedded resin for conductive particle inspection. An ion milling apparatus (IM 4000 manufactured by hitachi high technology corporation) was used to cut a cross section of the conductive particles so as to pass through the vicinity of the center of the conductive particles dispersed in the embedding resin for inspection. Subsequently, the presence or absence of the conductive metal in the cross section of the base material particles was measured by an energy dispersive X-ray analyzer (EDS) using a field emission transmission electron microscope (manufactured by japan electronics corporation, "JEM-2010 FEF"), whereby a distribution result of the conductive metal in the particle diameter direction of the base material particles was obtained. The first ratio and the second ratio can be calculated from the distribution result of the conductive metal in the arbitrarily selected 20 conductive particles.
The binder resin is not particularly limited. As the binder resin, a known insulating resin can be used. The adhesive resin preferably contains a thermoplastic component (thermoplastic compound) or a curable component, and more preferably contains a curable component. Examples of the curable component include a photocurable component and a thermosetting component. The photocurable component preferably contains a photocurable compound and a photopolymerization initiator. The thermosetting component preferably contains a thermosetting compound and a thermosetting agent.
Examples of the binder resin include vinyl resins, thermoplastic resins, curable resins, thermoplastic block copolymers, and elastomers. The binder resin may be used alone or in combination of two or more.
Examples of the vinyl resin include vinyl acetate resin, acrylic resin, and styrene resin. Examples of the thermoplastic resin include polyolefin resins, ethylene-vinyl acetate copolymers, and polyamide resins. Examples of the curable resin include epoxy resins, polyurethane resins, polyimide resins, and unsaturated polyester resins. The curable resin may be a room temperature curable resin, a thermosetting resin, a photo curable resin, or a moisture curable resin. The curable resin may be used together with a curing agent. Examples of the thermoplastic block copolymer include styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block copolymer, hydrogenated product of styrene-butadiene-styrene block copolymer, hydrogenated product of styrene-isoprene-styrene block copolymer, and the like. Examples of the elastomer include styrene-butadiene copolymer rubber and acrylonitrile-styrene block copolymer rubber.
The conductive material may contain various additives such as a filler, an extender, a softener, a plasticizer, a polymerization catalyst, a curing catalyst, a colorant, an antioxidant, a heat stabilizer, a light stabilizer, an ultraviolet absorber, a lubricant, an antistatic agent, and a flame retardant, in addition to the conductive particles and the binder resin.
As a method for dispersing the conductive particles in the binder resin, a conventionally known dispersing method can be used, and is not particularly limited. As a method for dispersing the conductive particles in the binder resin, the following method and the like can be mentioned. And a method in which the conductive particles are added to the binder resin, and then kneaded and dispersed by using a planetary mixer or the like. A method in which the conductive particles are uniformly dispersed in water or an organic solvent using a homogenizer or the like, and then added to the binder resin, and kneaded and dispersed using a planetary mixer or the like. The binder resin is diluted with water, an organic solvent, or the like, and then the conductive particles are added thereto, and the mixture is kneaded and dispersed by using a planetary mixer or the like.
The viscosity (. Eta.25) of the conductive material at 25℃is preferably 30 Pa.s or more, more preferably 50 Pa.s or more, and preferably 400 Pa.s or less, more preferably 300 Pa.s or less. If the viscosity of the conductive material at 25 ℃ is not less than the lower limit and not more than the upper limit, the insulation reliability between the electrodes can be further effectively improved, and the conduction reliability between the electrodes can be further effectively improved. The viscosity (. Eta.25) can be appropriately adjusted depending on the kind of the compounding ingredients and the compounding amount.
The viscosity (. Eta.25) can be measured, for example, using an E-type viscometer (TVE 22L manufactured by Tokyo Co., ltd.) at 25℃and 5 rpm.
The conductive material according to the present invention can be used as a conductive paste, a conductive film, or the like. If the conductive material according to the present invention is a conductive film, a film containing no conductive particles may be stacked on the conductive film containing conductive particles. The conductive paste is preferably an anisotropic conductive paste. The conductive film is preferably an anisotropic conductive film.
The content of the binder resin in 100 wt% of the conductive material is preferably 10 wt% or more, more preferably 30 wt% or more, further preferably 50 wt% or more, particularly preferably 70 wt% or more, and preferably 99.99 wt% or less, more preferably 99.9 wt% or less. When the content of the binder resin is not less than the lower limit and not more than the upper limit, the conductive particles can be efficiently arranged between the electrodes, and the connection reliability of the members to be connected by the conductive material can be further improved.
The content of the conductive particles in the conductive material is preferably 0.01 wt% or more, more preferably 0.1 wt% or more, and preferably 80 wt% or less, more preferably 60 wt% or less, further preferably 40 wt% or less, particularly preferably 20 wt% or less, and most preferably 10 wt% or less, based on 100 wt% of the conductive material. When the content of the conductive particles is not less than the lower limit and not more than the upper limit, the connection resistance between the electrodes can be further effectively reduced. When the content of the conductive particles is not less than the lower limit and not more than the upper limit, the conduction reliability and insulation reliability between the electrodes can be further improved.
(Connection Structure)
The connection structure according to the present invention comprises: the first connection object member includes a first electrode on a surface thereof, a second connection object member includes a second electrode on a surface thereof, and a connection portion connecting the first connection object member and the second connection object member. In the connection structure according to the present invention, the material of the connection portion is the conductive particles or a conductive material containing the conductive particles and a binder resin. In the connection structure according to the present invention, the first electrode and the second electrode are electrically connected by the conductive particles.
The connection structure may be obtained by a step of disposing the conductive particles or the conductive material between the first connection target member and the second connection target member, and a step of performing conductive connection by thermocompression bonding. When the conductive particles contain the insulating material, the insulating material is preferably detached from the conductive particles during the thermocompression bonding.
If the conductive particles are used alone, the connection portion itself is the conductive particle. That is, the first member to be connected and the second member to be connected are connected by the conductive particles. The conductive material used to obtain the connection structure is preferably an anisotropic conductive material.
Fig. 5 is a front cross-sectional view schematically showing a connection structure using conductive particles according to the first embodiment of the present invention.
The connection structure 51 shown in fig. 5 includes: a first member to be connected 52, a second member to be connected 53, and a connecting portion 54 connecting the first and second members to be connected 52, 53. The connection portion 54 is formed by curing the conductive material containing the conductive particles 1. In fig. 5, the conductive particles 1 are schematically shown for convenience of illustration. Other conductive particles such as the conductive particles 11 and 21 may be used instead of the conductive particles 1.
The first connection object member 52 has a plurality of first electrodes 52a on its surface (upper surface). The second connection object member 53 has a plurality of second electrodes 53a on its surface (lower surface). The first electrode 52a and the second electrode 53a are electrically connected by 1 or more conductive particles 1. Therefore, the first and second members to be connected 52, 53 are electrically connected by the conductive particles 1.
The method for manufacturing the connection structure is not particularly limited. As an example of a method for manufacturing the connection structure, there is given: and a method in which the conductive material is disposed between the first member to be connected and the second member to be connected, and then the laminate is heated and pressed. The pressure of the thermocompression bonding is preferably 40MPa or more, more preferably 60MPa or more, and preferably 90MPa or less, more preferably 70MPa or less. The heating temperature of the thermocompression bonding is preferably 80 ℃ or higher, more preferably 100 ℃ or higher, and preferably 140 ℃ or lower, more preferably 120 ℃ or lower. If the pressure and temperature of the thermocompression bonding are not less than the lower limit and not more than the upper limit, the conduction reliability and insulation reliability between the electrodes can be further improved. Further, if the conductive particles have the insulating particles, the insulating particles can be easily detached from the surfaces of the conductive particles at the time of conducting connection.
When the conductive particles include the insulating particles, the conductive particles and the insulating particles existing between the first electrode and the second electrode can be removed when the laminate is heated and pressurized. For example, the conductive particles and the insulating particles existing between the first electrode and the second electrode can be easily separated from the surface of the conductive particles when the heating and the pressing are performed. When the heating and pressing are performed, a part of the insulating particles are separated from the surface of the conductive particles, and a part of the surface of the conductive portion is exposed. The exposed portion of the surface of the conductive portion is in contact with the first electrode and the second electrode, whereby the first electrode and the second electrode can be electrically connected via the conductive particles.
In the connection structure according to the present invention, since the conductive particles are used, by compressing the conductive particles when the heating and the pressing are performed, not only can conductive paths be formed on the surfaces (conductive portions) of the conductive particles, but also conductive paths can be formed by bringing conductive metals inside the conductive particles into contact with each other. As a result, even when the thickness of the conductive portion is small, the connection resistance between the electrodes in the up-down direction can be sufficiently reduced. Further, since the thickness of the conductive portion is small, aggregation of conductive particles can be suppressed, and insulation reliability between laterally adjacent electrodes which cannot be connected can be effectively improved.
The first and second members to be connected are not limited. The first and second connection target members include, specifically, electronic components such as semiconductor chips, semiconductor packages, LED chips, LED packages, capacitors, and diodes, and electronic components such as resin films, printed circuit boards, flexible printed boards, flexible flat cables, rigid and flexible boards, glass epoxy boards, and circuit boards such as glass boards. The first connection target member and the second connection target member are preferably electronic components.
Examples of the electrode provided on the connection target member include metal electrodes such as a gold electrode, a nickel electrode, a tin electrode, an aluminum electrode, a copper electrode, a molybdenum electrode, a silver electrode, an SUS electrode, and a tungsten electrode. When the connection target member is a flexible printed board, the electrode is preferably a gold electrode, a nickel electrode, a tin electrode, a silver electrode, or a copper electrode. When the connection target member is a glass substrate, the electrode is preferably an aluminum electrode, a copper electrode, a molybdenum electrode, a silver electrode, or a tungsten electrode. When the electrode is an aluminum electrode, the electrode may be an electrode made of aluminum alone or an electrode in which an aluminum layer is laminated on the surface of a metal oxide layer. Examples of the material of the metal oxide layer include indium oxide doped with a trivalent metal element and zinc oxide doped with a trivalent metal element. Examples of the trivalent metal element include Sn, al, and Ga.
Hereinafter, the present invention will be specifically described with reference to examples and comparative examples. The present invention is not limited to the following examples.
Example 1
(1) Preparation of substrate particles
Polystyrene particles having an average particle diameter of 0.5 μm were prepared as seed particles. 3.9 parts by weight of the above polystyrene particles, 500 parts by weight of ion-exchanged water, and 120 parts by weight of a 5% by weight aqueous polyvinyl alcohol solution were mixed to prepare a mixed solution. After dispersing the above mixed solution by using ultrasonic waves, putting the mixed solution into a liquid separating bottle, and stirring until uniform.
Subsequently, 150 parts by weight of divinylbenzene (monomer component), 2 parts by weight of 2,2' -azobis (methyl isobutyrate) (manufactured by Wako pure chemical industries, ltd. "V-601"), and 2 parts by weight of benzoyl peroxide (manufactured by Nikko Co., ltd. "Niper BW") were mixed. In addition, 9 parts by weight of triethanolamine lauryl sulfate, 50 parts by weight of toluene (solvent), and 1100 parts by weight of ion-exchanged water were added to prepare an emulsion.
The emulsion was added to the above-mentioned mixed solution in a liquid-separating bottle in several portions, and stirred for 12 hours to allow the seed particles to absorb the monomer, thereby obtaining a suspension containing the seed particles swollen with the monomer.
Subsequently, 490 parts by weight of a 5% by weight aqueous polyvinyl alcohol solution was added, heating was started and reacted at 85℃for 9 hours, to obtain base particles having a particle diameter of 2.0. Mu.m.
(2) Preparation of conductive particles
After the obtained base material particles were washed and dried, 10 parts by weight of the base material particles were dispersed in 1000 parts by weight of an alkaline solution containing 5% by weight of a palladium catalyst liquid using an ultrasonic disperser, and then the solution was filtered to remove the base material particles. Subsequently, the substrate particles were added to 100 parts by weight of a1 wt% dimethylamine borane solution to activate the surfaces of the substrate particles. After the surface-activated base particles were sufficiently washed, they were dispersed in 500 parts by weight of distilled water, to obtain a dispersion. Next, 1g of nickel particle slurry (average particle diameter 100 nm) was added to the above dispersion for 3 minutes to obtain a suspension containing base particles to which a core material was attached.
In addition, a nickel plating solution (pH 8.5) containing 0.35mol/L nickel sulfate, 1.38mol/L dimethylamine borane, and 0.5mol/L sodium citrate was prepared.
The obtained suspension was stirred at 60℃and 300 parts by weight of the nickel plating solution was slowly dropped into the suspension, whereby electroless nickel plating was performed. Subsequently, the particles were removed by filtering the suspension, washed and dried, thereby forming a nickel-boron conductive layer on the surface of the substrate particles, and conductive particles having conductive portions on the surface were obtained.
(3) Preparation of conductive Material (Anisotropic conductive paste)
The obtained conductive particles were mixed with 7 parts by weight of bisphenol a type phenoxy resin, 25 parts by weight of fluorene type epoxy resin, 4 parts by weight of phenol novolac type epoxy resin, 30 parts by weight of phenol novolac type epoxy resin, and SI-60L (manufactured by san new chemical industry co., ltd.) and subjected to defoaming for 3 minutes, followed by stirring, whereby a conductive material (anisotropic conductive paste) was obtained.
(4) Preparation of connection Structure
A transparent glass substrate having an IZO electrode pattern (the first electrode, the metal on the electrode surface had a Vickers hardness of 100 Hv) with an L/S of 10 μm/10 μm formed on the upper surface was prepared. Further, a semiconductor chip having an Au electrode pattern (second electrode, metal of the electrode surface having a Vickers hardness of 50 Hv) with an L/S of 10 μm/10 μm formed on the lower surface was prepared. The obtained anisotropic conductive paste was applied to the transparent glass substrate to a thickness of 30 μm, thereby forming an anisotropic conductive paste layer. Subsequently, the above semiconductor chip is laminated on the anisotropic conductive paste layer in such a manner that the electrodes are opposed to each other. Then, the pressure heating head was placed on the upper surface of the semiconductor chip while adjusting the temperature of the pressure heating head so that the anisotropic conductive paste layer became 100 ℃, and a pressure of 85MPa was applied to cure the anisotropic conductive paste layer at 100 ℃, thereby obtaining a connection structure.
Example 2
Conductive particles, conductive materials, and connection structures were obtained in the same manner as in example 1, except that the blending amount of the solvent was adjusted to 10 parts by weight at the time of preparing the base particles.
Example 3
Conductive particles, conductive materials, and connection structures were obtained in the same manner as in example 1, except that the blending amount of the solvent was adjusted to 70 parts by weight at the time of preparing the base particles.
Example 4
A conductive material and a connection structure were obtained in the same manner as in example 1, except that the blending amount of the base particles was adjusted to 5 parts by weight in the preparation of the conductive particles.
Example 5
A conductive material and a connection structure were obtained in the same manner as in example 1, except that the blending amount of the base particles was adjusted to 2.5 parts by weight in the preparation of the conductive particles.
Example 6
The conductive particles obtained in example 1 were prepared. Further, a gold plating solution was prepared in which 5g of potassium gold cyanide was added to 500g of a solution containing 10g/L of ethylenediamine 4 sodium acetate and 10g/L of sodium citrate. 10 parts by weight of the conductive particles obtained in example 1 were added to 500 parts by weight of a gold plating solution, and immersed at 70℃for 30 minutes to perform electroless gold plating. Subsequently, the particles were removed by filtering the suspension, washed and dried, thereby forming a nickel-boron-gold conductive layer on the surface of the substrate particles, and conductive particles having conductive portions on the surface were obtained. A conductive material and a connection structure were obtained in the same manner as in example 1, except that the obtained conductive particles were used.
Example 7
To 200 parts by weight of distilled water, 10 parts by weight of the conductive particles obtained in example 1 were added and dispersed, thereby obtaining a suspension. Further, a palladium plating solution containing 10g/L ethylenediamine, 3.0g/L palladium sulfate and 5.0g/L sodium formate was prepared. After the suspension was heated to 70 ℃, 700 parts by weight of the palladium plating solution was dropped over 10 minutes, whereby electroless palladium plating was performed. Subsequently, the particles were removed by filtering the suspension, washed and dried, thereby forming a nickel-boron-palladium conductive layer on the surface of the substrate particles, and conductive particles having conductive portions on the surface were obtained. A conductive material and a connection structure were obtained in the same manner as in example 1, except that the obtained conductive particles were used.
Example 8
To 200 parts by weight of distilled water, 10 parts by weight of the conductive particles obtained in example 1 were added and dispersed, thereby obtaining a suspension. Further, a mixed solution containing 10g/L of silver potassium cyanide and 80g/L of potassium cyanide, 5g/L of ethylenediamine tetraacetic acid, and 20g/L of sodium hydroxide was adjusted to pH6 with sodium hydroxide, whereby a silver plating solution was prepared. After heating the suspension to 50 ℃, 700 parts by weight of the silver plating solution was dropped over 30 minutes, whereby electroless silver plating was performed. Subsequently, the particles were removed by filtering the suspension, washed and dried, thereby forming a nickel-boron-silver conductive layer on the surface of the substrate particles, and conductive particles having conductive portions on the surface were obtained. A conductive material and a connection structure were obtained in the same manner as in example 1, except that the obtained conductive particles were used.
Example 9
In preparing the base material particles, by changing the particle diameter of the seed particles, base material particles having a particle diameter of 1.0 μm were obtained. Conductive particles, conductive materials, and connection structures were obtained in the same manner as in example 1, except that the obtained base particles were used and the amount of the obtained base particles used was changed to 5 parts by weight.
Example 10
In preparing the base material particles, by changing the particle diameter of the seed particles, base material particles having a particle diameter of 2.5 μm were obtained. Conductive particles, conductive materials, and connection structures were obtained in the same manner as in example 1, except that the obtained base particles were used and the amount of the obtained base particles used was changed to 12.5 parts by weight.
Example 11
In preparing the base material particles, by changing the particle diameter of the seed particles, base material particles having a particle diameter of 3.0 μm were obtained. Conductive particles, conductive materials, and connection structures were obtained in the same manner as in example 1, except that the obtained base particles were used and the amount of the obtained base particles used was changed to 15 parts by weight.
Example 12
In preparing the base material particles, by changing the particle diameter of the seed particles, base material particles having a particle diameter of 5.0 μm were obtained. Conductive particles, conductive materials, and connection structures were obtained in the same manner as in example 1, except that the obtained base particles were used and the amount of the obtained base particles used was changed to 25 parts by weight.
Example 13
In preparing the base material particles, by changing the particle diameter of the seed particles, base material particles having a particle diameter of 10.0 μm were obtained. Conductive particles, conductive materials, and connection structures were obtained in the same manner as in example 1, except that the obtained base particles were used and the amount of the obtained base particles used was changed to 50 parts by weight.
Example 14
(1) Preparation of insulating particles
The monomer composition was placed in a 1000mL bottle equipped with a four-port separable cap, stirring blade, three-way cock, cooling tube, and temperature probe, and distilled water was then added thereto to make the solid content of the monomer composition 10% by weight, and the mixture was stirred at 200rpm and polymerized at 60℃for 24 hours under a nitrogen atmosphere. The monomer composition contained 360mmol of methyl methacrylate, 45mmol of glycidyl methacrylate, 20mmol of p-styryldiethylphosphine, 13mmol of ethylene glycol dimethacrylate, 0.5mmol of polyvinylpyrrolidone, and 1mmol of 2,2' -azobis {2- [ N- (2-carboxyethyl) amidino ] propane }. After the completion of the reaction, freeze-drying was performed to obtain insulating particles (particle diameter: 360 nm) having phosphorus atoms derived from p-styryl diethyl phosphine on the surface.
(2) Preparation of conductive particles with insulating particles
The insulating particles obtained in (1) above were dispersed in distilled water under ultrasonic irradiation to obtain a 10 wt% aqueous dispersion of insulating particles. 10g of the conductive particles obtained in example 1 were dispersed in 500mL of distilled water, and 1g of a 10 wt% aqueous dispersion of insulating particles was added thereto, followed by stirring at room temperature for 8 hours. After filtration through a 3 μm mesh filter, the mixture was washed with methanol and dried to obtain conductive particles having insulating particles. A conductive material and a connection structure were obtained in the same manner as in example 1, except that the obtained conductive particles with insulating particles were used.
Example 15
Conductive particles, conductive materials, and connection structures were obtained in the same manner as in example 1, except that a nickel particle slurry (average particle diameter 100 nm) was not used in the preparation of conductive particles.
Example 16
Conductive particles, a conductive material, and a connection structure were obtained in the same manner as in example 1, except that the amount of the catalyst liquid was changed to 200 parts by weight at the time of preparing the conductive particles.
Example 17
Conductive particles, a conductive material, and a connection structure were obtained in the same manner as in example 1, except that the amount of the catalyst liquid was changed to 500 parts by weight at the time of preparing the conductive particles.
Example 18
The conductive particles obtained in example 15 were prepared. Using the conductive particles obtained in example 15, conductive particles with insulating particles were obtained in the same manner as in example 14. A conductive material and a connection structure were obtained in the same manner as in example 1, except that the obtained conductive particles with insulating particles were used.
Comparative example 1
Conductive particles, conductive materials, and connection structures were obtained in the same manner as in example 1, except that the solvent was changed from toluene to ethanol at the time of preparing the base particles.
Comparative example 2
Conductive particles, conductive materials, and connection structures were obtained in the same manner as in comparative example 1, except that the blending amount of the base particles was 5 parts by weight in the preparation of the conductive particles.
Comparative example 3
The conductive particles obtained in comparative example 2 were prepared. Using the conductive particles obtained in comparative example 2, conductive particles with insulating particles were obtained in the same manner as in example 14. A conductive material and a connection structure were obtained in the same manner as in example 1, except that the obtained conductive particles with insulating particles were used.
Comparative example 4
Conductive particles, conductive materials, and connection structures were obtained in the same manner as in comparative example 1, except that the blending amount of the base particles was 20 parts by weight in the preparation of the conductive particles.
(Evaluation)
(1) Particle diameter of base material particles and conductive particles
The particle diameters of the obtained base particles and conductive particles were calculated using a particle size distribution measuring apparatus (Multisizer 4 manufactured by Beckman Coulter). Specifically, the average value was calculated by measuring the particle diameter of about 100000 base material particles or conductive particles.
(2) BET specific surface area of base particles
For the obtained substrate particles, the adsorption isotherm of nitrogen was measured using "NOVA4200e" manufactured by Cantachrome Instruments company. According to the BET method, the specific surface area of the base material particles was calculated from the measurement results.
(3) Total pore volume of substrate particles
For the obtained substrate particles, the adsorption isotherm of nitrogen was measured using "NOVA4200e" manufactured by Cantachrome Instruments company. According to the BJH method, the total pore volume of the substrate particles is calculated from the measurement results.
(4) Average pore diameter of substrate particles
For the obtained substrate particles, the adsorption isotherm of nitrogen was measured using "NOVA4200e" manufactured by Cantachrome Instruments company. According to the BJH method, the average pore diameter of the base material particles is calculated from the measurement results.
(5) Porosity of the substrate particles
For the obtained substrate particles, the cumulative penetration amount of mercury with respect to the pressure applied by the mercury porosimeter "Poremaster" manufactured by Cantachrome Instruments company was measured. From the measurement results, the porosity of the base material particles was calculated.
(6) Content of conductive metal in 100% by volume of conductive particles
The content of the conductive metal in 100% by volume of the conductive particles was calculated by the following expression for the conductive particles obtained.
Content of conductive metal in 100 vol% of conductive particles (vol%) =d×m/Dmetal ×100
D: specific gravity of conductive particles
M: metallization ratio of conductive particles
Dmetal: specific gravity of conductive metal
The metallization ratio of the conductive particles was calculated using an ICP emission spectrometer (ICP-AES manufactured by horiba corporation). The specific gravity of the conductive particles was measured using a true specific gravity meter (manufactured by Shimadzu corporation, "Acupic"). The specific gravity of the conductive metal is calculated using a value unique to the metal.
(7) Conductive metal content in base particles in 100% by volume of conductive particles, and conductive metal content in conductive portions in 100% by volume of conductive particles
The content of the conductive metal contained in the conductive portion in 100% by volume of the conductive particles was calculated by the following expression.
The content (volume%) of the conductive metal contained in the conductive portion in 100 volume% of the conductive particles=d×m 1/Dmetal ×100
M 1: metallization ratio of conductive portion
Dmetal: specific gravity of conductive metal
The metallization ratio M 1 of the conductive portion refers to the content (g) of the conductive metal in the conductive portion contained in 1g of the conductive particles expressed by the ratio, that is, refers to the content (g) of the conductive metal in the conductive portion contained in 1g of the conductive particles/1 g of the conductive particles.
The metallization ratio M 1 of the conductive portion is calculated by the following two relational expressions.
A＝[(r+t)3-r3]d1/r3d2 (1)
A＝M1/(1-M1) (2)
R: radius of substrate particle
T: thickness of conductive part
D 1: specific gravity of conductive metal
D 2: specific gravity of base material particles
M 1: metallization ratio of conductive portion
Subsequently, the content of the conductive metal contained in the base material particles in 100% by volume of the conductive particles was calculated from the following expression for the conductive particles obtained.
The content of conductive metal contained in the base particle in 100% by volume of the conductive particle (volume%) =the content of conductive metal in 100% by volume of the conductive particle (volume%) —the content of conductive metal contained in the conductive portion in 100% by volume of the conductive particle (volume%) =d×m/Dmetal ×100-d×m 1/Dmetal×100＝D×(M-M1)/Dmetal ×100
D: specific gravity of conductive particles
M: metallization ratio of conductive particles
M 1: metallization ratio of conductive portion
Dmetal: specific gravity of conductive metal
(8) The ratio of the number of conductive particles of the conductive metal (first ratio and second ratio)
When a region having a distance of 1/2 of the particle diameter of the base material particles from the outer surface of the base material particles toward the center thereof is defined as a region R1, the ratio of the number of conductive particles having the conductive metal present in the region R1 of the base material particles to the total number of conductive particles of 100% (first ratio) is calculated by using the obtained conductive material. When the region of the substrate particles having a distance of 1/2 of the particle diameter from the center of the substrate particles toward the outer surface thereof is defined as a region R2, the ratio (second ratio) of the number of conductive particles having the conductive metal present in the region R2 of the substrate particles to the total 100% of the total number of conductive particles is calculated by using the obtained conductive material.
The conductive particles are recovered by filtering the resulting conductive material. The conductive particles were added to "Technobit4000,4000" manufactured by Kulzer corporation and dispersed so that the content of the recovered conductive particles was 30 wt%, to prepare an embedding resin for conductive particle inspection. An ion milling apparatus (IM 4000 manufactured by hitachi high technology corporation) was used to cut a cross section of one conductive particle so as to pass through the vicinity of the center of the conductive particle dispersed in the embedded resin for inspection. Subsequently, the presence or absence of the conductive metal in the cross section of the base material particles was measured by an energy dispersive X-ray analyzer (EDS) using a field emission transmission electron microscope (manufactured by japan electronics corporation, "JEM-2010 FEF"), whereby a distribution result of the conductive metal in the particle diameter direction of the base material particles was obtained. The first ratio and the second ratio are calculated from the distribution result of the conductive metal in the arbitrarily selected 20 conductive particles.
(9) Compressive elastic modulus of conductive particles
The compressive elastic modulus (10% K value and 30% K value) of the obtained conductive particles was measured by the method described above using a micro compression tester (Fisher scope H-100, manufactured by Fisher Co.). From the measurement results, 10% k value and 30% k value were calculated.
(10) Agglomeration of conductive particles
The obtained conductive material was observed to confirm whether or not aggregation of conductive particles occurred. The aggregation of the conductive particles was determined under the following conditions.
[ Criterion for determining aggregation of conductive particles ]
O: no aggregation of conductive particles occurs
Delta: the conductive particles are slightly aggregated
X: aggregation of conductive particles occurs
(11) Adhesion of conductive portions in conductive particles
1G of the obtained conductive particles and 50g of zirconia beads having a diameter of 1mm were put into a 100mL mayonnaise bottle. Subsequently, 10mL of toluene was added to the mayonnaise bottle. The inside of the mayonnaise bottle was stirred at 300rpm for 10 minutes using a stirrer (THREE-ONE MOTOR). After stirring, the conductive particles and the zirconia beads were separated, and the conductive particles were observed with a Scanning Electron Microscope (SEM) to confirm whether or not the conductive portions of the conductive particles were peeled off. The adhesion of the conductive portion in the conductive particle was determined under the following conditions.
[ Criterion for determining adhesion of conductive portions in conductive particles ]
O: the conductive part of the conductive particle is not peeled off
X: peeling of conductive portions in conductive particles
(12) Connecting resistance (electrode of upper and lower)
The connection resistances between the upper and lower electrodes of the obtained 20 connection structures were measured by the four-terminal method, respectively. The average value of the connection resistance was calculated. From the relationship of voltage=current×resistance, the connection resistance can be obtained by measuring the voltage when a constant current flows. The connection resistance was determined according to the following criteria.
[ Criterion for connecting resistance ]
O: the average value of the connection resistance is 1.5 Ω or less
O: the average value of the connection resistance is more than 1.5 omega and less than 2.0 omega
O: the average value of the connection resistance is more than 2.0 omega and less than 5.0 omega
Delta: the average value of the connection resistance is more than 5.0 omega and less than 10 omega
X: the average value of the connection resistance is more than 10 omega
(13) Insulation reliability (electrodes adjacent in transverse direction)
By measuring the resistance value using a tester, it was evaluated whether or not leakage between adjacent electrodes occurred in the 20 connection structures obtained in the evaluation of the connection reliability of (12) above. Insulation reliability was evaluated according to the following criteria.
O: the number of the connection structures with the resistance value of 10 8 omega or more is 20
O: the number of connection structures having a resistance value of 10 8 Ω or more is 18 or more and less than 20
O: the number of connection structures having a resistance value of 10 8 Ω or more is 15 or more and less than 18
Delta: the number of connection structures having a resistance value of 10 8 Ω or more is 10 or more and less than 15
X: the number of the connection structures with the resistance value of more than 10 8 omega is less than 10
The results are shown in tables 1 to 4 below.
TABLE 1
TABLE 2
TABLE 3
TABLE 4
Graphic symbol description
1. Conductive particles
2. Substrate particles
3. Conductive part
11. Conductive particles
11A projection
12. Conductive part
12A projection
13. Core material
14. Insulating material
21. Conductive particles
21A projection
22. Conductive part
22A projection
22A first conductive portion
22Aa projection
22B second conductive part
22Ba projection
51. Connection structure
52. First connecting object part
52A first electrode
53. Second connection object member
53A second electrode
54. Connecting part
Claims (15)
1. A conductive particle is provided with: a base particle, and a conductive portion disposed on a surface of the base particle,
The substrate particles are resin particles, or inorganic particles other than metal, or organic-inorganic mixed particles,
The base material particles contain a conductive metal inside the base material particles.
2. The conductive particle according to claim 1, wherein the porosity of the base particle is 10% or more.
3. The conductive particle according to claim 1 or 2, wherein the conductive metal contains nickel, gold, palladium, silver or copper.
4. The conductive particle according to claim 1 or 2, wherein the conductive portion contains nickel, gold, palladium, silver, or copper.
5. The conductive particle according to claim 1 or 2, wherein the conductive particle has a 10% k value of 100N/mm 2 or more and 25000N/mm 2 or less.
6. The conductive particle according to claim 1 or 2, wherein the conductive particle has a 30% k value of 100N/mm 2 or more and 15000N/mm 2 or less.
7. The conductive particle according to claim 1 or 2, wherein a ratio of a 10% k value of the conductive particle to a 30% k value of the conductive particle is 1.5 or more and 5 or less.
8. The conductive particle according to claim 1 or 2, wherein the conductive particle has a particle diameter of 0.1 μm or more and 1000 μm or less.
9. The conductive particle according to claim 1 or 2, wherein the content of the conductive metal contained in the base particle is 0.1% by volume or more and 30% by volume or less in 100% by volume of the conductive particle.
10. The conductive particle according to claim 1 or 2, which has a protrusion on an outer surface of the conductive portion.
11. The conductive particle according to claim 1 or 2, which has an insulating substance provided on an outer surface of the conductive portion.
12. An electroconductive material comprising the electroconductive particles according to any one of claims 1 to 11 and a binder resin.
13. The conductive material according to claim 12, which contains a plurality of the conductive particles,
When a region having a distance of 1/2 of the particle diameter of the base material particles from the outer surface of the base material particles toward the center thereof is defined as a region R1, the proportion of the number of conductive particles having the conductive metal present in the region R1 of the base material particles is 50% or more based on 100% of the total number of conductive particles.
14. The conductive material according to claim 12 or 13, which contains a plurality of the conductive particles,
When the region of 1/2 distance from the center of the base material particle to the particle diameter of the base material particle on the outer surface thereof is defined as a region R2, the proportion of the number of conductive particles having the conductive metal present in the region R2 of the base material particle is 5% or more, based on 100% of the total number of conductive particles.
15. A connection structure is provided with:
A first connection object member having a first electrode on a surface thereof,
A second connection object member having a second electrode on a surface thereof,
And a connection section for connecting the first connection object member and the second connection object member, wherein,
The material of the connecting portion is the conductive particles according to any one of claims 1 to 11, or a conductive material containing the conductive particles and a binder resin,
The first electrode and the second electrode are electrically connected by the conductive particles.
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