KR20180061084A - Method for manufacturing connection structure, conductive particle, conductive film and connection structure - Google Patents

Abstract

A method of manufacturing a connection structure capable of reducing a connection resistance between electrodes. A method for manufacturing a connection structure according to the present invention is a method for manufacturing a connection structure using a binder resin having a viscosity at 130 ° C of 50 Pa · s or more and 1000 Pa · s or less and a conductive film containing conductive particles, And a second connection member having a second electrode on a surface thereof is used as the object to be inspected and the conductive film is arranged so that the first electrode and the second electrode face each other, And a step of forming a connection structure by arranging the conductive particles between the object member and the object member to obtain a laminate, and heating and pressing and thermocompression bonding the laminate to obtain a connection structure, Is 5 or more per 500 mu m < ² > of the surface area of the first electrode.

Description

Method for manufacturing connection structure, conductive particle, conductive film and connection structure

The present invention relates to a method of manufacturing a connection structure for electrically connecting electrodes with conductive particles. The present invention also relates to conductive particles and a conductive film used for electrical connection between electrodes. Still further, the present invention relates to a connection structure using the conductive film containing the conductive particles.

Anisotropic conductive paste such as anisotropic conductive paste and anisotropic conductive film are widely known. In the anisotropic conductive material, a plurality of conductive particles are dispersed in the binder resin.

The anisotropic conductive material can be used for various types of connection structures such as a connection between a flexible printed circuit board and a glass substrate (FOG (Film on Glass), a connection between a semiconductor chip and a flexible printed circuit (COF (Chip on Film) ), A connection between a semiconductor chip and a glass substrate (COG (Chip on Glass)), and a connection between a flexible printed substrate and a glass epoxy substrate (FOB (Film on Board)).

For example, when an electrode of a semiconductor chip and an electrode of a glass substrate are electrically connected by the anisotropic conductive material, an anisotropic conductive material containing conductive particles is arranged on a glass substrate. Then, the semiconductor chips are stacked and heated and pressed. Thereby, the anisotropic conductive material is cured, and the electrodes are electrically connected via the conductive particles to obtain a connection structure.

As an example of the conductive particles, Patent Document 1 below discloses a method for manufacturing an anisotropic conductive film comprising a conductive layer in which conductive particles are arranged in a single layer on a surface portion and an insulating adhesive layer laminated on at least one surface of the conductive layer Method is disclosed. The coefficient of variation of the center-to-center distance of the conductive particles is 0.05 or more and 0.5 or less. The melting viscosity of the insulating adhesive constituting the insulating adhesive layer at 180 캜 is lower than the melt viscosity at 180 캜 of the binder resin constituting the conductive layer. (1) a step of producing a coating solution in which an insulating adhesive containing a thermosetting resin, a microcapsule-type curing agent, and a film-forming polymer is dissolved or dispersed in a solvent; (2) And (3) a film forming step of heating the releasable base material coated with the coating liquid in the elastic region of the releasable base material to volatilize the solvent.

Patent Document 2 discloses a resin composition comprising a first layer formed by a first resin composition comprising conductive particles, insulating particles and an insulating resin, and a second layer formed by a second resin composition comprising a curing agent and a curable insulating resin An anisotropic conductive film is disclosed. The first layer is present in a region within 1.5 times the average particle diameter of the conductive particles along the thickness direction from one side surface. The thickness of the thinnest portion of the first layer is smaller than the average particle diameter of the conductive particles. The melt viscosity of the first resin composition at 180 캜 is higher than the melt viscosity at 180 캜 of the second resin composition.

Japanese Patent Application Laid-Open No. 2010-248386 Japanese Patent Application Laid-Open No. 2010-9804

There is a problem that the connection resistance between the electrodes becomes high when the electrodes are electrically connected to each other using a conventional anisotropic conductive film as described in Patent Documents 1 and 2 to obtain a connection structure.

In recent years, in order to reduce the environmental load, even when the content of the conductive particles in the conductive film is decreased, and the viscosity of the binder resin in the conductive film is raised to about 130 캜, the conductive particles And development of a conductive film have been demanded.

An object of the present invention is to provide a method of manufacturing a connection structure capable of lowering the connection resistance between electrodes.

It is also an object of the present invention to provide a conductive particle capable of lowering the connection resistance between electrodes when a conductive film in which conductive particles are blended in a binder resin is used to electrically connect the electrodes. The present invention also provides a conductive film and a connection structure using the conductive particles.

Still further, an object of the present invention is to provide a conductive film which can lower the connection resistance between electrodes when the electrodes are electrically connected.

According to a broad aspect of the present invention, a binder resin having a viscosity at 130 占 폚 of 50 Pa · s or more and 1000 Pa · s or less and a conductive film containing conductive particles are used and a first connection object member having a first electrode on the surface thereof And a second electrode to be connected is used as the first electrode and the second electrode is on the surface so that the first electrode and the second electrode face each other and the conductive film is sandwiched between the first connection object member and the second connection object member To obtain a laminate, and a step of heating and pressing the laminate and thermocompression bonding the laminate to obtain a connection structure. In the resulting connection structure, the conductive particles are pressed into the first electrode And a number of indentations having a depth of 5 nm or more is 5 or more per 500 mu m ² of the surface area of the first electrode.

In a specific aspect of the method for manufacturing a connection structure according to the present invention, the first electrode contains Ti or Al and has a thickness of 1 占 퐉 or more and 2 占 퐉 or less.

In a specific aspect of the method for manufacturing a connection structure according to the present invention, the first electrode has a TiO 2 electrode portion having a thickness of 0.1 탆 or more and 0.5 탆 or less from the inner surface toward the outer surface, AlTi electrode portion and an IZO electrode portion having a thickness of 0.05 m or more and 0.2 m or less are laminated in this order, or the first electrode is a composite electrode having a thickness of 0.1 占 퐉 or more and 0.5 占 퐉 or less from the inner surface to the outer surface, An Al-Nd electrode portion having a thickness of 0.5 mu m or more and 2.0 mu m or less and an ITO electrode portion having a thickness of 0.05 mu m or more and 0.2 mu m or less in this order.

In a specific aspect of the method for manufacturing a connection structure according to the present invention, the first electrode has a TiO 2 electrode portion having a thickness of 0.1 μm or more and 0.5 μm or less and a TiO 2 electrode portion having a thickness of 0.5 μm or more and 2.0 μm or less, Electrode portion and an IZO electrode portion having a thickness of 0.05 m or more and 0.2 m or less are stacked in this order. In another specific aspect, the first electrode has a thickness of 0.1 mu m or more and 0.5 mu m or less An Al-Nd electrode portion having a thickness of 0.5 mu m or more and 2.0 mu m or less and an ITO electrode portion having a thickness of 0.05 mu m or more and 0.2 mu m or less in this order.

In a specific aspect of the method for manufacturing a connection structure according to the present invention, a connection structure in which the connection resistance between the first electrode and the second electrode is 1.5 Ω or less is obtained.

According to a broad aspect of the present invention, there is provided a conductive particle used for obtaining a conductive film, which is blended in a binder resin, wherein the conductive particle has a binder resin having a viscosity at 130 캜 of 110 賊 10 Pa 揃 s, Wherein a conductive film containing the conductive particles is used in an amount of 1 g / cm 3 or less and a bump electrode containing Ti or Al and having a thickness of 1 μm or more and 2 μm or less as a first electrode, And a second connection object member having an Au bump electrode on the surface thereof as a second electrode is used and the conductive film is sandwiched between the first connection object member and the second connection object member so that the first electrode and the second electrode face each other, When the connection structure was obtained by thermocompression bonding for 10 seconds at a temperature of 130 캜 and a total pressure of 70 MPa for the total area of the connection portions of the bump electrodes, Wherein the number of indentations having a depth of 5 nm or more at which the conductive particles are pressed into the first electrode is 5 or more per 500 mu m ² of the surface area of the first electrode.

In a specific aspect in which the conductive particles according to the present invention are present, the conductive particles are conductive particles used for obtaining a conductive film by being compounded in a binder resin having a viscosity at 130 ° C of 50 Pa · s or more and 1000 Pa · s or less.

According to a broad aspect of the present invention, there is provided a conductive film comprising a binder resin having a viscosity at 130 占 폚 of 50 Pa · s or more and 1000 Pa · s or less and the above-described conductive particles.

According to a broad aspect of the present invention, there is provided a liquid crystal display device including a first connection target member having a first electrode on a surface thereof, a second connection target member having a second electrode on a surface thereof, Wherein the conductive film has the above-mentioned conductive film, and the first electrode and the second electrode are electrically connected to each other by the conductive particles.

In a specific aspect of the connection structure according to the present invention, the connection resistance between the first electrode and the second electrode is 1.5 Ω or less.

According to a broad aspect of the present invention, there is provided a conductive film comprising a binder resin having a viscosity at 130 ° C of not less than 50 Pa · s and not more than 1000 Pa · s and conductive particles, wherein the conductive film contains Ti or Al A first connection object member having a bump electrode having a thickness of 1 mu m or more and 2 mu m or less on a surface thereof is used and a second connection object member having an Au bump electrode on its surface is used as a second electrode, And the conductive film is disposed between the first connection target member and the second connection target member so as to face the second electrode and thermocompression bonding is performed for 10 seconds at a temperature of 130 占 폚 and a pressure of 70 MPa per the total area of the connection portion of the bump electrode when connected to the structure obtained, the connection structure of the first electrode is the conductive particles 5 per number of press-in depth than the ^second surface area 500㎛ 5nm indentation of the first electrode in the in the resultant The conductive film of the conductive film having the least value is provided.

A method for manufacturing a connection structure according to the present invention is a method for manufacturing a connection structure using a binder resin having a viscosity at 130 ° C of 50 Pa · s or more and 1000 Pa · s or less and a conductive film containing conductive particles, And a second connection member having a second electrode on a surface thereof is used as the object to be inspected and the conductive film is arranged so that the first electrode and the second electrode face each other, And a step of forming a connection structure by arranging the conductive particles between the object member and the object member to obtain a laminate, and heating and pressing and thermocompression bonding the laminate to obtain a connection structure, The number of indentations having a depth of 5 nm or more is 5 or more per 500 mu m ² of the surface area of the first electrode. Thus, the connection resistance between the electrodes can be reduced.

The conductive particles according to the present invention use a binder resin having a viscosity of 100 ± 10 Pa · s at 130 ° C. and a conductive film containing the conductive particles at a content of 30000 ± 2500 particles / , A first connection target member having a bump electrode having Ti or Al and a thickness of not less than 1 mu m and not more than 2 mu m on its surface is used and a second connection target member having an Au bump electrode on its surface as a second electrode And the conductive film is disposed between the first connection target member and the second connection target member so that the first electrode and the second electrode face each other, , The number of indentations having a depth of 5 nm or more at which the conductive particles are pressed into the first electrode in the obtained connection structure has a surface area of 5 00㎛ Since conductive particles represent a value equal to or greater than 5 per ^second, using the conductive particles blended in the binder resin in the conductive film, in case of electrically connecting the electrodes, it is possible to lower the connection resistance between the electrodes.

The conductive film according to the present invention comprises a binder resin having a viscosity of not less than 50 Pa · s and not more than 1000 Pa · s at 130 ° C and conductive particles and the conductive film contains Ti or Al as a first electrode, A first connection object member having a bump electrode having a thickness of 2 mu m or less and a second connection object member having a Au bump electrode on the surface thereof is used as the second electrode, The conductive film was disposed between the first connection target member and the second connection target member so that the two electrodes were opposed to each other and thermocompression was performed for 10 seconds at a temperature of 130 캜 and a pressure of 70 MPa per the total area of the connection portion of the bump electrode, the time gained, the more the number of the conductive particles is 5nm the indentation depth to the first electrode indentation, five or more value per specific surface area 500㎛ ² of the first electrode in the connection structure thus obtained or Since the conductive film is provided, the connection resistance between the electrodes can be reduced when the electrodes are electrically connected.

1 is a cross-sectional view showing a conductive particle according to a first embodiment of the present invention.
2 is a cross-sectional view showing a conductive particle according to a second embodiment of the present invention.
3 is a cross-sectional view showing a conductive particle according to a third embodiment of the present invention.
4 is a front sectional view schematically showing a connection structure using conductive particles according to the first embodiment of the present invention.

Hereinafter, the details of the present invention will be described.

In recent years, development of conductive particles and conductive films capable of lowering the connection resistance between electrodes even if the content of the conductive particles in the conductive film is reduced in order to reduce the environmental load is required. In order to arrange the conductive particles as much as possible between the electrodes while reducing the content of the conductive particles in the conductive film, it is necessary that the conductive particles disposed between the electrodes before compression are prevented from flowing between the electrodes at the time of compression bonding. In order to suppress the outflow of the conductive particles, it is preferable to increase the viscosity of the binder resin at the time of compression, and the viscosity of the binder resin at 130 DEG C is preferably 50 Pa · s or more. On the other hand, from the viewpoint of suppressing the occurrence of voids after compression, it is preferable to lower the viscosity of the binder resin at the time of compression, and the viscosity of the binder resin at 130 占 폚 is preferably 1000 Pa · s or less.

The compression bonding is generally carried out at a temperature of 100 ° C or higher and 200 ° C or lower. In recent years, low temperature bonding at 150 ° C or lower has become mainstream, and the melt viscosity of the binder resin near 130 ° C greatly affects the outflow of the conductive particles It is easy to go crazy.

In the examination of the present inventors, it was difficult to make the connection resistance sufficiently low only by relatively increasing the viscosity of the binder resin at 130 캜. The inventors of the present invention have found that when a binder resin having a relatively high viscosity at 130 占 폚 is used, the binder resin between the conductive particles and the electrode is removed together with the binder resin, It is necessary to use conductive particles having properties capable of forming a predetermined indentation on the electrode so as to crush the oxide film of the electrode.

A method for manufacturing a connection structure according to the present invention is a method for manufacturing a connection structure using a binder resin having a viscosity at 130 ° C of 50 Pa · s or more and 1000 Pa · s or less and a conductive film containing conductive particles, A second member to be connected is used which has a second electrode on the surface thereof and a target member. The method for manufacturing a connection structure according to the present invention is characterized in that the conductive film is disposed between the first connection target member and the second connection target member such that the first electrode and the second electrode face each other, And a step of heating and pressing the laminate and thermocompression bonding the laminate to obtain a connection structure. In the connection structure according to the present invention, the number of indentations having a depth of 5 nm or more at which the conductive particles are pressed into the first electrode is 5 or more per 500 m ² of the surface area of the first electrode, .

The conductive particles according to the present invention are conductive particles used in combination with a binder resin to obtain a conductive film. The conductive particles according to the present invention use a binder resin having a viscosity of 110 ± 10 Pa · s at 130 ° C. and a conductive film containing the conductive particles at a content of 30000 ± 2500 particles / A first connection target member having a bump electrode containing Ti or Al and having a thickness of 1 mu m or more and 2 mu m or less is used and a second connection target member having an Au bump electrode on the surface thereof is used as a second electrode And the conductive film is disposed between the first connection object member and the second connection object member so that the first electrode and the second electrode face each other and the conductive film is formed at a temperature of 130 占 폚 and a total area of 70 MPa The number of indentations having a depth of 5 nm or more at which the conductive particles are pressed into the first electrode in the obtained connection structure obtained by thermocompression bonding with pressure for 10 seconds, And is a conductive particle showing a value of 5 or more per ² mu m.

In the conductive particle according to the present invention, the conductive film for measuring the number of indentations is made to specify the conductive particle itself. In the conductive particles according to the present invention, the measurement of the number of indentations is measured to specify the conductive particles themselves. When the connection structure is manufactured using the conductive particles according to the present invention, the connection structure may not be obtained under the above-described manufacturing conditions for specifying the conductive particles themselves.

In the conductive particles according to the present invention, the conductive particles may not be used in a content of 30000 ± 2500 / 중에 in the conductive film, and the conductive particles may be used in the conductive film in a content of 30000 ± 5000 /.. If the content of the conductive particles is 30,000 ± 2500 pieces /,, the number of the indentations in the first electrode in the connection structure is not greatly different. The conductive particles according to the present invention may not be used dispersedly in a binder resin having a viscosity of 100 Pa · s at 130 ° C or may be dispersed in a binder resin having a viscosity at 130 ° C of 50 Pa · s or more and 1000 Pa · s or less .

In order to obtain the connection structure for measuring the number of indentations in the conductive particles according to the present invention, the connection structure is thermocompression bonded at a pressure of 130 MPa and a total area of 70 MPa at the connection portion of the bump electrode. This thermocompression bonding condition is also a condition for producing a connection structure for specifying the conductive particles themselves or the conductive film itself in the conductive particles according to the present invention and the conductive film according to the present invention.

In the conductive particles according to the present invention, the conductive particles are not required to be thermocompression-bonded at 130 DEG C and 70 MPa of the total area of the connection portion of the bump electrode, in order to fabricate the connection structure. The thermocompression bonding is preferably carried out at a temperature of 100 DEG C or more and 150 DEG C or less by thermocompression bonding at a pressure of 50 MPa or more per total area of the connecting portion of the bump electrode and 90 MPa or less of the total area of the connecting portion of the bump electrode. When the bump is not used at the time of thermocompression bonding, the pressure can be set at 3 MPa per total area of the pressure bonding instead of 70 MPa per the total area of the connection portion of the bump electrode. Also in this case, the pressure is preferably 1 MPa or more and 5 MPa or less per total area of the compression bonding. The same applies to the conductive film according to the present invention.

The conductive film according to the present invention includes a binder resin having a viscosity at 130 ° C of 50 Pa · s or more and 1000 Pa · s or less and conductive particles. The conductive film according to the present invention uses a first connection target member having a bump electrode having Ti or Al and a thickness of 1 mu m or more and 2 mu m or less as a first electrode, A second connection object member having a bump electrode on a surface thereof is used and the conductive film is disposed between the first connection object member and the second connection object member so that the first electrode and the second electrode face each other, Pressed at 130 DEG C for 10 seconds at a pressure of 3 MPa per total area of the compression bonding or a total area of 70 MPa of the total area of the connection portion of the bump electrode to obtain the connection structure, the conductive particles were pressed into the first electrode in the obtained connection structure And the number of indentations having a depth of 5 nm or more is 5 or more per 500 mu m ² of the surface area of the first electrode.

In the conductive film according to the present invention, the measurement of the number of indentations is measured to specify the conductive film itself. When the connection structure is manufactured using the conductive film according to the present invention, the connection structure may not be obtained under the above-described manufacturing conditions for specifying the conductive film itself.

In order to obtain a connection structure for measuring the number of indentations, the conductive film according to the present invention may be thermocompression-bonded at 130 占 폚 and a pressure of 3 MPa per total area of the compression bonding, or at 130 占 폚 and a total area And thermocompression is performed at a pressure of 70 MPa. This thermocompression bonding condition is also a condition for producing a connection structure for specifying the conductive particles themselves or the conductive film itself in the conductive particles according to the present invention and the conductive film according to the present invention.

In the conductive film according to the present invention, the conductive film may be thermally pressed at 130 占 폚 and a total pressure of 3 MPa or 70 MPa for the total area of the connection portion of the bump electrode in order to manufacture the connection structure. The thermocompression bonding is preferably carried out at a temperature of 150 DEG C or less and is thermocompression bonded at a pressure of 1 MPa or more per total area of the pressure bonding or at least 50 MPa per total area of the connecting portion of the bump electrode and 5 MPa or less per total area of the pressure bonding, .

The bump electrode is an electrode protruding from the member to be connected. The total area of the connecting portions of the bump electrodes is not limited to the area of the portion in contact with the conductive particles but is not limited to the area of the connecting portion between the first connecting object member and the connecting portion and the second connecting object member, Means the total area of the portions where the electrodes face each other. The total crimped area refers to the total area of the crimped areas when viewed from the plane (when viewed in the stacking direction of the first connection target member and the connection portion and the second connection target member), the total of the portions of the first connection target member and the second connection target member Area.

In the present invention, since the above-described structure is provided, a connection structure having a low connection resistance between electrodes can be obtained. Particularly, even when a conductive film having relatively high viscosity of binder resin at 130 占 폚 and having a relatively small content of conductive particles is used, since a predetermined indentation is formed on the electrode, the connection resistance is lowered.

In the method for producing the connection structure and the binder resin for dispersing the conductive particles and the conductive film, the viscosity of the binder resin at 130 ° C is preferably 50 Pa · s or more, and preferably 1000 Pa · s or less . From the viewpoint of effectively lowering the connection resistance, the viscosity of the binder resin at 130 캜 is more preferably 70 Pa · s or more, and still more preferably 500 Pa · s or less.

The viscosity of the binder resin at 130 占 폚 is measured using a viscoelasticity measuring device ("AR-2000ex" manufactured by TA Instruments).

In the conductive film, the content of the conductive particles is preferably 30,000 ± 5000 pieces / □, more preferably 30,000 ± 2500 pieces / □.

It is preferable that the electrode shape for measuring the number of indents is an electrode pattern having an L / S of 20 mu m / 20 mu m which is a line (a portion where an electrode is formed) / a space (a portion where no electrode is formed).

In order to obtain a connection structure for measuring the number of indentations, the substrate is thermocompression bonded at a pressure of 130 MPa at a temperature of 130 DEG C and a total area of 5 MPa or a total area of the bonded portion of the bump electrode. This thermocompression bonding condition is also a condition for producing a connection structure for specifying the conductive particles themselves or the conductive film itself in the conductive particles according to the present invention and the conductive film according to the present invention.

It is preferable that the conductive particles and the conductive film are thermocompression bonded at a temperature of 100 ° C or more and 150 ° C or less in order to fabricate a connection structure. The thermocompression bonding is preferably performed at a pressure of 1 MPa or more per unit area of the bonded portion of the bump electrode, It is preferable to perform thermocompression bonding at a pressure of 5 MPa per area or a pressure of 90 MPa or less per a total area of the connecting portion of the bump electrode.

In the conductive particles and the conductive film, the number of the indentations is 5 or more per 500 mu m ² of the surface area of the first electrode. The number of the indentations is preferably 8 or more, more preferably 10 or more per 500 mu m ² of the surface area of the first electrode. The upper limit of the number of the indentations is not particularly limited, and the number of the indentations becomes a certain value or less depending on the content of the conductive particles. The number of the indentations is, for example, 25 or less per 500 mu m ² of the surface area of the first electrode.

In the connection structure, the number of the indentations is 5 or more per 500 mu m ² of the surface area of the first electrode. The number of the indentations is preferably 8 or more, more preferably 10 or more per 500 mu m ² of the surface area of the first electrode. The upper limit of the number of the indentations is not particularly limited, and the number of the indentations becomes a certain value or less depending on the content of the conductive particles. The number of the indentations is, for example, 25 or less per 500 mu m ² of the surface area of the first electrode.

From the viewpoint of further effectively lowering the connection resistance or reducing the variation of the connection resistance between the plurality of electrodes, it is preferable that the conductive particles are uniformly disposed between the electrodes. The present inventors have found that when a binder resin having a relatively high viscosity at 130 DEG C is used, the binder resin between the conductive particles and the electrode is removed together with the binder resin, and the oxide particles It is possible to lower the connection resistance more effectively or reduce variations in the connection resistance between the plurality of electrodes by using the conductive particles having the property of squashing the conductive particles and uniformly arranging them between the electrodes.

From the viewpoint of further effectively lowering the connection resistance and uniformly arranging the conductive particles between the electrodes, the conductive particles according to the present invention have a binder resin having a viscosity at 130 ° C of 110 ± 10 Pa · s and a binder resin having a viscosity of 30000 ± 2500 Wherein a conductive film containing the conductive particles is used in an amount of 1 g / cm 3 or less and a bump electrode containing Ti or Al and having a thickness of 1 μm or more and 2 μm or less as a first electrode, And a second connection object member having an Au bump electrode on the surface thereof as a second electrode is used and the conductive film is sandwiched between the first connection object member and the second connection object member so that the first electrode and the second electrode face each other, And the connecting structure was obtained by thermocompression bonding at 130 DEG C and a pressure of 70 MPa per the total area of the connecting portion of the bump electrode for 10 seconds, When the number of the conductive particles disposed on the surface area per 500㎛ ² of the first electrode, measured in at 100 places, the number of CV value of the conductive particles in the measurement at the 100 locations of 25% or less Is preferably a conductive particle.

In the conductive particle according to the present invention, the conductive film for measuring the CV value is prepared so as to specify the conductive particle itself. In the conductive particle according to the present invention, the measurement of the CV value is carried out so as to specify the conductive particle itself. When the connection structure is manufactured using the conductive particles according to the present invention, the connection structure may not be obtained under the above-described manufacturing conditions for specifying the conductive particles themselves.

From the viewpoint of further effectively lowering the connection resistance and uniformly arranging the conductive particles between the electrodes, the conductive film according to the present invention has a binder resin having a viscosity at 130 ° C of 50 Pa · s or more and 1000 Pa · s or less, . A conductive film according to the present invention uses a first connection target member having a bump electrode having Ti or Al and a thickness of 1 mu m or more and 2 mu m or less as a first electrode, Wherein the conductive film is disposed between the first connection target member and the second connection target member so that the first electrode and the second electrode face each other, when the scored ℃ the connecting element and the total compression per 10 seconds hot pressing a pressure of 70MPa total area of the connection portion of 3MPa or bump electrodes, disposed on the surface area per 500㎛ ² of the first electrode in the connection structure obtained And the number CV of the conductive particles in the measured value at 100 points when the number of the conductive particles measured at 100 points is 25% or less desirable.

In the conductive film according to the present invention, the measurement of the CV value is performed to specify the conductive film itself. When the connection structure is manufactured using the conductive film according to the present invention, the connection structure may not be obtained under the above-described manufacturing conditions for specifying the conductive film itself.

From the viewpoint of lowering the connection resistance still more effectively and evenly distribute the conductive particles between the electrodes, the method of manufacturing the connecting element according to the present invention, the first batch of ² per surface area 500㎛ electrode in the obtained connection structure It is preferable to obtain a connecting structure in which the CV value of the number of the conductive particles in the measured value at 100 points is 25% or less when the number of the conductive particles is measured at 100 points.

In the conductive particles and the conductive film, the CV value is preferably 25% or less. From the viewpoint of effectively lowering the connection resistance, the CV value is more preferably 20% or less, and further preferably 17% or less. The lower limit of the CV value is not particularly limited, and the smaller the CV value, the better.

In the above connection structure, the CV value is preferably 25% or less. From the viewpoint of effectively lowering the connection resistance, the CV value is more preferably 20% or less, and further preferably 17% or less. The lower limit of the CV value is not particularly limited, and the smaller the CV value, the better.

The first electrode is preferably a bump electrode. The second electrode is preferably a bump electrode.

The first electrode is preferably a bump electrode containing Ti or Al and having a thickness of 1 mu m or more and 2 mu m or less. The first electrode containing Ti or Al preferably includes both Ti and Al. More specifically, the first electrode has a TiO 2 electrode portion having a thickness of 0.1 μm or more and 0.5 μm or less, an AlTi electrode portion having a thickness of 0.5 μm or more and 2.0 μm or less, (Composite electrode A) in which the following IZO electrode portions are laminated in this order or a Mo electrode portion having a thickness of 0.1 占 퐉 or more and 0.5 占 퐉 or less and a thickness of 0.5 占 퐉 or more and 2.0 占 퐉 or less (Composite electrode B) in which an Al-Nd electrode portion of a thickness of 0.05 to 0.2 mu m and an ITO electrode portion of a thickness of 0.05 to 0.2 mu m are stacked in this order is preferable. From the inner surface to the outer surface, (Composite electrode A ') in which an electrode portion, an AlTi electrode portion having a thickness of 1.0 占 퐉, and an IZO electrode portion having a thickness of 0.10 占 퐉 are stacked in this order, or alternatively, from the inner surface to the outer surface, Mo electrode portion and a 1.0 占 퐉 thick Al (Composite electrode B ') in which an -Nd electrode portion and an ITO electrode portion having a thickness of 0.1 mu m are stacked in this order. The first electrode may be the composite electrode A, the composite electrode B, the composite electrode A ', or the composite electrode B'. Also, when the number of the indentations in the composite electrode A or the composite electrode B is indicated, even if electrodes other than the composite electrode A and the composite electrode B are used, the connection resistance is sufficiently low. Further, when the CV value of the composite electrode A or the composite electrode B is shown, even if electrodes other than the composite electrode A and the composite electrode B are used, the connection resistance is further effectively lowered. In the connection structure, the conductive particles and the conductive film, electrodes other than the above may be used to obtain the connection structure.

(10% K value) when the conductive particles are compressed by 10% is preferably at least 5000 N / mm 2, more preferably at least 10,000 N / mm 2 from the viewpoint of effectively lowering the connection resistance (Constitution 1) . The 10% K value is preferably 20000 N / mm 2 or less, and more preferably 15000 N / mm 2 or less.

The 10% K value of the conductive particles can be measured as follows.

One conductive particle is compacted under the condition of applying a test load of 90 mN at 25 DEG C and a maximum test load of 30 mN on the smooth indenter end face of a cylindrical column (diameter 50 mu m, made of diamond) by using a micro compression tester. At this time, the load value N and the compression displacement (mm) are measured. From the obtained measured values, the above-described compressive modulus can be obtained by the following formula. As the micro compression tester, for example, "Fisher Scope H-100" manufactured by Fisher Co., Ltd. or the like is used.

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

F: load value (N) when the conductive particles are compression-deformed by 10%

S: Compressive displacement (mm) when conductive particles are compressed and deformed by 10%

R: radius of conductive particle (mm)

From the viewpoint of effectively lowering the connection resistance, it is preferable that the conductive particles have a plurality of protrusions on the outer surface of the conductive portion (Constitution 2).

From the viewpoint of effectively lowering the connection resistance, it is preferable that the conductive particles have a conductive portion including nickel (Constitution 3). From the viewpoint of effectively lowering the connection resistance, the thickness of the conductive portion including nickel is preferably 100 nm or more, and more preferably 150 nm or more. The thickness of the conductive portion including nickel is preferably 250 nm or less.

From the viewpoint of effectively lowering the connection resistance, two or more conductive portions (conductive layers) may be provided (Configuration 4). From the viewpoint of effectively lowering the connection resistance, it is preferable that the conductive portion of two or more layers has a conductive portion including nickel.

From the viewpoint of effectively lowering the connection resistance, it is preferable that the conductive particles have a core material embedded in the conductive portion (Constitution 5). The Mohs hardness of the material of the core material is preferably larger than the Mohs hardness of the material of the conductive portion.

From the viewpoint of effectively lowering the connection resistance, the conductive particles include a first conductive portion having no projections on the outer surface, a second conductive portion having a plurality of projections on the outer surface thereof, (Structure 6).

From the viewpoint of effectively lowering the connection resistance, it is preferable that the outermost conductive part contains at least 99 wt% of one metal atom (constitution 7).

From the viewpoint of effectively lowering the connection resistance, it is preferable that the conductive particles include organic-inorganic hybrid particles as the base particles (Constitution 8).

From the viewpoint of effectively lowering the connection resistance, it is preferable that in the conductive particle, the base particles are hardened from the inside to the outside (Constitution 9).

From the viewpoint of enhancing insulation reliability, it is preferable that the conductive particles include an insulating material disposed on the outer surface of the conductive portion (Configuration 10).

The conductive particles, the conductive film and the connection structure of the present invention can be produced by appropriately combining and adjusting the above-mentioned constitution, the materials, constitution and others to be described below within a range that can be practiced by those skilled in the art. The effects of the present invention can be obtained for the first time.

In the conductive particles, the conductive film and the connection structure of the present invention, it is preferable that the conductive particles include the above-described constitutions 1 and 2, more preferably the constitutions 1, 2, 3 and 5, 2, 3, 5, and 10, respectively. In addition, particularly preferable examples of the conductive particles having the structures 1 to 8 and 10, the conductive particles having the structures 1 to 7, 9 and 10, and the conductive particles having both of the structures 1 to 10 have.

Hereinafter, the conductive particles, the conductive film, the connection structure and the method of manufacturing the connection structure will be described in more detail.

In the following description, "(meth) acryl" means one or both of "acrylic" and "methacryl", and "(meth) acrylate" means either One or both.

(Conductive particles)

The conductive particle may be a conductive particle as a whole, or may be a conductive particle having a base particle and a conductive section disposed on the surface of the base particle. From the viewpoint of increasing the contact area between the electrode and the conductive particles and effectively lowering the connection resistance, it is preferable that the conductive particles include base particles and a conductive portion disposed on the surface of the base particles.

Hereinafter, referring to the drawings, the conductive particles will be specifically described. The present invention is not limited to the following embodiments, and the following embodiments may be appropriately modified, improved, or the like so long as the features of the present invention are not impaired.

1 is a cross-sectional view showing a conductive particle according to a first embodiment of the present invention.

The conductive particles 1 shown in Fig. 1 have base particles 2 and conductive portions 3. Fig. The conductive part 3 is disposed on the surface of the base particle 2. In the first embodiment, the conductive portion 3 is in contact with the surface of the base particle 2. The conductive particles (1) are coated particles in which the surface of the base particles (2) is covered with the conductive parts (3). In the conductive particle 1, the conductive portion 3 is a single conductive portion (conductive layer).

The conductive particles 1 are different from the conductive particles 11 and 21 described later and do not have a core material. The conductive particles 1 do not have projections on the conductive surface and do not have projections on the outer surface of the conductive portion 3. [ The conductive particles (1) are spherical.

As described above, the conductive particles may not have protrusions on the conductive surface, may not have protrusions on the outer surface of the conductive portion, or may be spherical. The conductive particles 1 are different from the conductive particles 11 and 21 described later, and do not have an insulating material. However, the conductive particles (1) may have an insulating material disposed on the outer surface of the conductive portion (3).

2 is a cross-sectional view showing a conductive particle according to a second embodiment of the present invention.

The conductive particles 11 shown in Fig. 2 have base particles 2, conductive portions 12, a plurality of core materials 13, and a plurality of insulating materials 14. The conductive part 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 particle 11, the conductive portion 12 is a conductive portion (conductive layer) of a single layer.

The conductive particles 11 have a plurality of projections 11a on the conductive surface. In the conductive particle 11, the conductive portion 12 has a plurality of projections 12a on its outer surface. A plurality of core materials (13) are arranged on the surface of the substrate particles (2). A plurality of core materials (13) are embedded in the conductive part (12). The core material 13 is disposed inside the projections 11a and 12a. The conductive part 12 covers a plurality of core materials 13. The outer surface of the conductive portion 12 is raised by the plurality of core materials 13 and the projections 11a and 12a are formed.

The conductive particles 11 have an insulating material 14 disposed on the outer surface of the conductive portion 12. At least a part of the outer surface of the conductive part 12 is covered with the insulating material 14. [ The insulating material 14 is formed of a material having an insulating property and is insulating particles. As described above, the conductive particles according to the present invention may have an insulating material disposed on the outer surface of the conductive portion. However, the conductive particles according to the present invention do not necessarily have an insulating material.

3 is a cross-sectional view showing the conductive particle according to the third embodiment of the present invention.

The conductive particles 21 shown in Fig. 3 have base particles 2, conductive portions 22, a plurality of core materials 13, and a plurality of insulating materials 14. The conductive portion 22 has a first conductive portion 22A on the base particle 2 side and a second conductive portion 22B on the opposite side of the base particle 2 side.

The conductive particles (11) and the conductive particles (21) differ only in conductive portions. That is, in the conductive particles 11, the conductive portions 12 having a one-layer structure are formed, whereas in the conductive particles 21, the first conductive portions 22A and the second conductive portions 22B Is formed. 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 particle 2. A 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. [ Therefore, 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 projections 21a on the conductive surface. In the conductive particles 21, the conductive portions 22 have a plurality of projections 22a on the outer surface. The first conductive portion 22A has a protrusion 22Aa on its outer surface. The second conductive portion 22B has a plurality of projections 22Ba on its outer surface. In the conductive particles 21, the conductive portions 22 are two conductive portions (conductive layers).

[Substrate Particle]

Examples of the base particles include resin particles, inorganic particles other than metal particles, organic-inorganic hybrid particles and metal particles. The base particles are preferably base particles excluding metal particles, more preferably resin particles, inorganic particles other than metal particles, or organic-inorganic hybrid particles. The base particles may be core shell particles.

The base particles are more preferably resin particles or organic-inorganic hybrid particles, and may be resin particles or organic-inorganic hybrid particles. By using these preferable base particles, conductive particles more suitable for electrical connection between electrodes can be obtained.

When the electrodes are connected using the conductive particles, the conductive particles are disposed between the electrodes, and then compressed to compress the conductive particles. When the base particles are resin particles or organic-inorganic hybrid particles, the conductive particles are liable to be deformed at the time of pressing, and the contact area between the conductive particles and the electrodes becomes large. As a result, the connection resistance between the electrodes is further reduced.

As the material of the resin particles, various organic materials are suitably used. Examples of the material of the resin particles include polyolefin resins such as polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinylidene chloride, polyisobutylene, and polybutadiene; Acrylic resins such as polymethyl methacrylate and polymethyl acrylate; Phenol resin, melamine resin, urea resin, benzoguanamine formaldehyde resin, urea formaldehyde resin, phenol resin, melamine resin, benzoguanamine resin, urea resin, urea resin, It is possible to use various polymerizable monomers having an epoxy resin, an unsaturated polyester resin, a saturated polyester resin, a polysulfone, a polyphenylene oxide, a polyacetal, a polyimide, a polyamideimide, a polyetheretherketone, a polyether sulfone and an ethylenic unsaturated group , And polymers obtained by polymerizing two or more of them. It is possible to design and synthesize resin particles having physical properties at the time of compression suitable for the conductive film and to control the hardness of the base particles to a suitable range easily so that the material of the resin particles has a plurality of ethylenically unsaturated groups Is preferably a polymer obtained by polymerizing one or more polymerizable monomers.

When the resin particle is obtained by polymerizing a polymerizable monomer having an ethylenic unsaturated group, examples of the polymerizable monomer having an ethylenic unsaturated group include a monomer that is incompatible with the monomer and a monomer that is crosslinkable.

Examples of the non-crosslinkable monomer include styrene-based monomers such as styrene and? -Methylstyrene; Carboxyl group-containing monomers such as (meth) acrylic acid, maleic acid, and maleic anhydride; (Meth) acrylate, ethyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl Alkyl (meth) acrylate compounds such as acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate and isobornyl (meth) acrylate; (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 monomers such as trifluoromethyl (meth) acrylate, pentafluoroethyl (meth) acrylate, vinyl chloride, vinyl fluoride and chlorostyrene.

Examples of the crosslinkable monomer include tetramethylolmethane tetra (meth) acrylate, tetramethylol methane tri (meth) acrylate, tetramethylol methane di (meth) acrylate, trimethylolpropane tri (meth) (Meth) acrylate, dipentaerythritol penta (meth) acrylate, glycerol tri (meth) acrylate, glycerol di (meth) acrylate, (poly) ethylene glycol di Polyfunctional (meth) acrylate compounds such as (meth) acrylate, (poly) propylene glycol di (meth) acrylate, (poly) tetramethylene glycol di (meth) acrylate and 1,4-butanediol di (meth) acrylate; (Meth) acryloxypropyltrimethoxysilane, trimethoxysilylstyrene, trimethylolpropane trimethoxysilane, triallyl trimellitate, divinyl benzene, diallyl phthalate, diallyl acrylamide, diallyl ether, , Silane-containing monomers such as vinyltrimethoxysilane, and the like.

The above-mentioned resin particles can be obtained by polymerizing the above-mentioned polymerizable monomer having an ethylenic unsaturated group by a known method. Examples of the method include suspension polymerization in the presence of, for example, a radical polymerization initiator, and polymerization by swelling the monomer together with the radical polymerization initiator using non-crosslinked seed particles.

When the base particles are inorganic particles other than metal particles or organic-inorganic hybrid particles, examples of the inorganic material that is the material of the base particles include silica, alumina, barium titanate, zirconia and carbon black. The inorganic material is preferably not a metal. The particles formed by the silica are not particularly limited. For example, particles obtained by hydrolyzing a silicon compound having two or more hydrolyzable alkoxysilyl groups to form crosslinked polymer particles, and then firing if necessary, . 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 type organic-inorganic hybrid particles having a core and a shell disposed on the surface of the core. The core is preferably an organic core. Preferably, the shell is an inorganic shell. From the viewpoint of effectively lowering the connection resistance between the electrodes, 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.

As the material of the organic core, resins and the like which are the materials of the above-mentioned resin particles can be mentioned.

Examples of the material of the inorganic shell include inorganic materials for forming the base particles described above. The material of the inorganic shell is preferably silica. It is preferable that the inorganic shell is formed on the surface of the core by converting the metal alkoxide into a shell-like material by a sol-gel method, and then firing the shell-like material. The metal alkoxide is preferably a silane alkoxide. The inorganic shell is preferably formed by silane alkoxide.

In the case where the base particles are metal particles, metals which are the material of the metal particles include silver, copper, nickel, silicon, gold, and titanium. However, it is preferable that the base particles are not metal particles.

The particle diameter of the base particles is preferably 0.1 μm or more, more preferably 1 μm or more, still more preferably 1.5 μm or more, particularly preferably 2 μm or more, preferably 1000 μm or less, More preferably not more than 500 mu m, further preferably not more than 50 mu m, further preferably not more than 30 mu m, particularly preferably not more than 5 mu m, and most preferably not more than 3 mu m. When the particle diameter of the base particles is not lower than the lower limit, the contact area between the conductive particles and the electrode becomes larger, so that the reliability of the conduction between the electrodes is further increased, and the connection resistance between the electrodes connected via the conductive particles is further lowered . Further, when the conductive part is formed on the surface of the substrate particles by electroless plating, it is difficult to coagulate and the coagulated conductive particles are hardly formed. When the particle diameter of the base particles is less than the upper limit, the conductive particles are easily compressed sufficiently, the connection resistance between the electrodes is further lowered, and the interval between the electrodes is reduced.

The particle diameter of the base particles indicates the diameter when the base particles are spherical, and the maximum diameter when the base particles are not spherical.

Particularly preferably, the particle size of the base particles is 1 탆 or more and 5 탆 or less. If the particle size of the base particles is in the range of 1 to 5 占 퐉, small conductive particles can be obtained even if the distance between the electrodes is small and the thickness of the conductive part is large.

[Conductive part]

The metal for forming the conductive part is not particularly limited. Examples of the metal include gold, silver, palladium, ruthenium, rhodium, osmium, iridium, copper, platinum, zinc, iron, tin, lead, aluminum, cobalt, indium, nickel, chromium, titanium, antimony, bismuth, , Germanium, cadmium, silicon, and alloys thereof. Examples of the metal include indium tin oxide (ITO) and solder. Among them, an alloy including tin, nickel, palladium, copper or gold is preferable, and nickel or palladium is preferable because the connection resistance between the electrodes can be further lowered.

Like the conductive particles 1 and 11, the conductive part may be formed by one layer. Like the conductive particles 21, the conductive portion may be formed by a plurality of layers. That is, the conductive portion may have a laminated structure of two or more layers. When the conductive part is formed by a plurality of layers, the outermost layer is preferably an alloy layer including a gold layer, a nickel layer, a palladium layer, a copper layer, or a tin and silver layer, more preferably a gold layer. When the outermost layer is the preferable conductive layer, the connection resistance between the electrodes is further lowered. Further, when the outermost layer is a gold layer, the corrosion resistance is further increased.

The particle diameter of the conductive particles is preferably 0.5 占 퐉 or more, more preferably 1 占 퐉 or more, preferably 520 占 퐉 or less, more preferably 500 占 퐉 or less, still more preferably 100 占 퐉 or less, Is not more than 50 mu m, particularly preferably not more than 20 mu m. When the particle diameters of the conductive particles are not less than the lower limit and not more than the upper limit, when the electrodes are connected using the conductive particles, the contact area between the conductive particles and the electrode becomes sufficiently large, . Further, the distance between the electrodes connected via the conductive particles is not excessively large, and the conductive portion is difficult to peel off from the surface of the base particles. When the particle diameter of the conductive particles is not less than the lower limit and not more than the upper limit, the conductive particles can be suitably used for the conductive film.

The particle diameter of the conductive particles means the diameter when the conductive particles are spherical, and the maximum diameter when the conductive particles have shapes other than the sphericity.

The thickness of the conductive portion (the thickness of the entire conductive portion) is preferably 0.005 탆 or more, more preferably 0.01 탆 or more, preferably 10 탆 or less, more preferably 1 탆 or less, further preferably 0.5 탆 or less , Particularly preferably not more than 0.3 mu m. The thickness of the conductive portion is the total thickness of the conductive layer when the conductive portion has multiple layers. When the thickness of the conductive part is not less than the lower limit and not more than the upper limit, sufficient conductivity is obtained, and the conductive particles are not too hard, and the conductive particles are sufficiently deformed at the time of connection between the electrodes.

When the conductive portion is a plurality of layers, the thickness of the conductive layer in the outermost layer is preferably 0.001 탆 or more, more preferably 0.01 탆 or more, preferably 0.5 탆 or less, and more preferably 0.1 탆 or less. If the thickness of the conductive layer in the outermost layer is not less than the lower limit and not more than the upper limit, the coating of the outermost conductive layer becomes uniform, the corrosion resistance becomes sufficiently high, and the connection resistance between the electrodes becomes further lower. Further, when the outermost layer is a gold layer, the thinner the thickness of the gold layer, the lower the cost.

The thickness of the conductive portion can be measured by observing the cross section of the conductive particles using, for example, a transmission electron microscope (TEM).

From the viewpoint of effectively increasing the conductivity, it is preferable that the conductive particles have a conductive portion including nickel. The content of nickel is preferably 50% by weight or more, more preferably 65% by weight or more, still more preferably 70% by weight or more, still more preferably 75% by weight or more in 100% by weight of the conductive part including nickel , Still more preferably not less than 80 wt%, particularly preferably not less than 85 wt%, particularly preferably not less than 90 wt%. In 100 wt% of the conductive part including nickel, the content of nickel is preferably 100 wt% or less, 99 wt% or less, or 95 wt% or less. When the content of nickel is not less than the above lower limit, the connection resistance between the electrodes is further lowered. Further, when the oxide film on the surface of the electrode or the conductive portion is small, the connection resistance between the electrodes tends to decrease as the content of nickel increases.

As a method for measuring the content of the metal contained in the conductive portion, various known analytical methods can be used without particular limitation. As the measuring method, an absorption analysis method or a spectrum analysis method can be mentioned. In the above absorption spectrophotometry, a frame absorption spectrophotometer, an electric heating spectrophotometer, or the like can be used. Examples of the spectrum analysis method include a plasma luminescence analysis method and a plasma ion mass spectrometry method.

When measuring the average content of the metal contained in the conductive portion, it is preferable to use an ICP emission spectrometer. Commercially available products of the ICP emission spectrometer include ICP emission spectrometers manufactured by HORIBA.

The conductive portion may contain phosphorus or boron in addition to nickel. Further, the conductive portion may include a metal other than nickel. When a plurality of metals are included in the conductive portion, a plurality of metals may be alloyed.

The content of phosphorus or boron is preferably 0.1% by weight or more, more preferably 1% by weight or more, and preferably 10% by weight or less, and still more preferably 10% by weight or less in 100% by weight of the conductive part containing nickel and phosphorus or boron 5% by weight or less. If the content of phosphorus or boron is lower than the above lower limit and above the upper limit, the resistance of the conductive part is further lowered, and the conductive part contributes to reduction of the connection resistance.

[Core material]

It is preferable that the conductive particles have protrusions on the conductive surface. It is preferable that the conductive particles have protrusions on the outer surface of the conductive portion. It is preferable that the projections are plural. In many cases, an oxide film is formed on the surface of the electrode connected by the conductive particles. In many cases, an oxide film is formed on the surface of the conductive portion of the conductive particles. By the use of the conductive particles having the projections, the conductive particles are disposed between the electrodes, and then the conductive particles are pressed, whereby the oxide film is effectively removed by the projections. As a result, the electrode and the conductive particle can be brought into more reliable contact with each other, and the connection resistance between the electrodes can be lowered. In addition, the binder resin between the conductive particles and the electrode can be effectively removed, and the effect is further enhanced in the present invention using a binder having a relatively high viscosity at 130 캜. In addition, when the conductive particles have an insulating material on the surface, the resin between the conductive particles and the electrode can be effectively removed by the protrusions of the conductive particles. As a result, the conduction reliability between the electrodes is further enhanced.

Since the core material is embedded in the conductive portion, it is easy to make the conductive portion have a plurality of protrusions on the outer surface. However, in order to form protrusions on the conductive surface of the conductive particles and the surface of the conductive portion, the core material may not necessarily be used.

Examples of the method for forming the projections include a method of attaching a core material to the surface of base particles and then forming a conductive part by electroless plating; a method of forming a conductive part by electroless plating on the surface of base particles, A method of forming a conductive portion by electroless plating and a method of adding a core material in a step of forming a conductive portion by electroless plating on the surface of base particles.

Examples of the material of the core material include a conductive material and a non-conductive material. Examples of the conductive material include metals, oxides of metals, conductive base metals such as graphite, and conductive polymers. Examples of the conductive polymer include polyacetylene and the like. Examples of the non-conductive material include silica, alumina, barium titanate, and zirconia. Among them, a metal is preferable because the conductivity can be increased and the connection resistance can be effectively lowered. The core material is preferably a metal particle. As the metal material of the core material, a metal exemplified as the material of the conductive film can be suitably used.

The shape of the core material is not particularly limited. The shape of the core material is preferably massive. As the core material, for example, there can be mentioned a lump of particles, a coagulated mass aggregated by a plurality of microparticles, and a lump of an irregular shape.

The average diameter (average particle diameter) of the core material is preferably 0.001 탆 or more, more preferably 0.05 탆 or more, preferably 0.9 탆 or less, and more preferably 0.2 탆 or less. If the average diameter of the core material is above the lower limit and below the upper limit, the connection resistance between the electrodes is effectively lowered.

The " average diameter (average particle diameter) " of the core material indicates a number average diameter (number average particle diameter). The average diameter of the core material is obtained by observing 50 pieces of any core material with an electron microscope or an optical microscope and calculating an average value.

The number of the projections per conductive particle is preferably 3 or more, and more preferably 5 or more. The upper limit of the number of the projections is not particularly limited. The upper limit of the number of the projections can be appropriately selected in consideration of the particle diameter of the conductive particles and the like.

The average height of the plurality of projections is preferably 0.001 탆 or more, more preferably 0.05 탆 or more, preferably 0.9 탆 or less, and more preferably 0.2 탆 or less. When the average height of the projections is not less than the lower limit and not more than the upper limit, the connection resistance between the electrodes is effectively lowered.

[Insulating material]

The conductive particles preferably include an insulating material disposed on an outer surface of the conductive portion. In this case, when conductive particles are used for connection between electrodes, it is possible to further prevent a short circuit between adjacent electrodes. Specifically, when a plurality of conductive particles are brought into contact with each other, an insulating material is present between the plurality of electrodes, so that it is possible to prevent a short circuit between the adjacent electrodes in the lateral direction, not between the upper and lower electrodes. Further, at the time of connection between the electrodes, the conductive particles of the conductive particles and the insulating material between the electrodes can be easily excluded by pressing the conductive particles with the two electrodes. When the conductive particles have a plurality of protrusions on the outer surface of the conductive portion, the insulating material between the conductive portions of the conductive particles and the electrode can be more easily excluded.

It is preferable that the insulating material is insulating particles in that the insulating material can be more easily removed at the time of pressing between the electrodes.

Specific examples of the insulating resin that is the material of the insulating material include polyolefins, (meth) acrylate polymers, (meth) acrylate copolymers, block polymers, crosslinked products of thermoplastic resins, thermoplastic resins, thermosetting resins and water- .

The average diameter (average particle diameter) of the insulating material can be appropriately selected according to the particle diameter of the conductive particles and the use of the conductive particles. The average diameter (average particle diameter) of the insulating material is preferably 0.005 탆 or more, more preferably 0.01 탆 or more, preferably 1 탆 or less, and more preferably 0.5 탆 or less. When the average diameter of the insulating material is not less than the lower limit, conductive portions of a plurality of conductive particles are less likely to come into contact with each other when the conductive particles are dispersed in the binder resin. When the average diameter of the insulating particles is less than the upper limit, since the insulating material between the electrodes and the conductive particles is removed at the time of connection between the electrodes, there is no need to set the pressure too high, and it is not necessary to heat at high temperature.

The " average diameter (average particle diameter) " of the insulating material indicates a number average diameter (number average particle diameter). The average diameter of the insulating material is obtained by using a particle size distribution measuring device or the like.

(Conductive film)

The conductive film according to the present invention includes the above-mentioned conductive particles and a binder resin. The binder resin is a component excluding the conductive particles in the conductive film. The conductive particles are dispersed in the binder resin and used as a conductive film. The conductive film is preferably an anisotropic conductive film. The conductive particles and the conductive film are used for electrical connection between the electrodes, respectively. The conductive film is preferably a circuit connecting material.

The binder resin is not particularly limited. As the binder resin, a known insulating resin is used. The binder resin preferably comprises a thermoplastic component or a curable component. The curable component may have photo-curability or may have a thermosetting property. The curable component may include a photocurable compound and a photopolymerization initiator, and may include a thermosetting compound and a thermosetting agent, and may include a photocurable compound, a photopolymerization initiator, a thermosetting compound, and a thermosetting agent.

Examples of the binder resin include a vinyl resin, a thermoplastic resin, a curable resin, a thermoplastic block copolymer and an elastomer. 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 a polyolefin resin, an ethylene-vinyl acetate copolymer and a polyamide resin. Examples of the curable resin include an epoxy resin, a urethane resin, a polyimide resin and an unsaturated polyester resin. 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 in combination with a curing agent. Examples of the thermoplastic block copolymer include a styrene-butadiene-styrene block copolymer, a styrene-isoprene-styrene block copolymer, a hydrogenated product of a styrene-butadiene-styrene block copolymer, and a hydrogenated product of a styrene-isoprene- Additives and the like. Examples of the elastomer include styrene-butadiene copolymer rubber and acrylonitrile-styrene block copolymer rubber.

The conductive film and the binder resin preferably include a thermoplastic component or a thermosetting component. The conductive film and the binder resin may include a thermoplastic component or may include a thermosetting component. The conductive film and the binder resin preferably include a thermosetting component. The thermosetting component preferably includes a curing compound that can be cured by heating and a thermosetting agent. The curable compound that can be cured by the heating and the thermosetting agent are used at a proper blending ratio such that the binder resin is cured.

The conductive film may contain various additives such as fillers, extenders, softeners, plasticizers, polymerization catalysts, curing catalysts, colorants, antioxidants, heat stabilizers, light stabilizers, ultraviolet absorbers, lubricants, antistatic agents and flame retardants do.

(Connection structure)

By using the conductive film containing the conductive particles and the binder resin to connect the members to be connected, a connection structure can be obtained.

Wherein the connection structure includes a first connection object member, a second connection object member, and a connection portion connecting the first and second connection object members, wherein the connection portion is a connection structure formed by the conductive film . In the case where conductive particles are used, the connection portion itself is conductive particles. That is, the first and second connection target members are connected by the conductive particles.

4 is a front sectional view schematically showing a connection structure using conductive particles according to a first embodiment of the present invention.

The connection structure 51 shown in Fig. 4 has a structure in which the first connection target member 52, the second connection target member 53 and the connection portion connecting the first and second connection target members 52 and 53 (54). The connecting portion 54 is formed by curing a conductive film containing the conductive particles 1. [ In Fig. 4, the conductive particles 1 are shown roughly in the figure for convenience of illustration. Instead of the conductive particles 1, the conductive particles 11 and 21 may be used.

The first connection target member 52 has a plurality of first electrodes 52a on its surface (upper surface). The second connection target 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 to each other by one or more conductive particles 1. [ Therefore, the first and second connection target members 52 and 53 are electrically connected by the conductive particles 1. [ An indentation (depression) in which the conductive particles 1 are press-fitted is formed in the first electrode. The indentation is so small that it is not shown in Fig.

The manufacturing method of the connection structure is not particularly limited. As an example of the manufacturing method of the connection structure, a method of arranging the conductive film between the first connection target member and the second connection target member, obtaining a laminate, heating and pressing the laminate, . The pressure of the pressurization is about 9.8 x 10 ⁴ to 4.9 x 10 ⁶ Pa. The temperature of the heating is about 120 to 220 占 폚.

Specifically, examples of the member to be connected include electronic parts such as a semiconductor chip, a capacitor and a diode, and electronic parts such as a printed circuit board, a flexible printed circuit board, a glass epoxy substrate and a circuit board such as a glass substrate. The connection target member is preferably an electronic component. The conductive particles are preferably used for electrical connection of electrodes in electronic parts.

Examples of the electrode provided on the member to be connected include metal electrodes such as a gold electrode, a nickel electrode, a tin electrode, an aluminum electrode, a copper electrode, a silver electrode, a molybdenum electrode, and a tungsten electrode. When the connection target member is a flexible printed circuit board, the electrode is preferably a gold electrode, a nickel electrode, a tin 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, or a tungsten electrode. When the electrode is an aluminum electrode, it may be an electrode formed only of aluminum, or an electrode in which an aluminum layer is laminated on the surface of the 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 described in detail with reference to examples and comparative examples. The present invention is not limited to the following examples.

(Example 1)

Preparation of conductive particles:

Divinylbenzene copolymer resin particles (Micropearl SP-203, manufactured by Sekisui Chemical Co., Ltd.) having a particle size of 3.0 占 퐉 were prepared. 10 parts by weight of the resin particles were dispersed in 100 parts by weight (100 g) of an alkali solution containing 5% by weight of a palladium catalyst solution by using an ultrasonic disperser, and the solution was filtered to take out the resin particles. Subsequently, the resin particles were added to 100 parts by weight of a 1 wt% solution of dimethylamine borane to activate the surface of the resin particles. The surface-activated resin particles were sufficiently washed with water and then added to 500 parts by weight of distilled water and dispersed to obtain a suspension. Subsequently, 1 g of metallic nickel particle slurry (average particle diameter 100 nm) was added for 3 minutes to the dispersion to obtain base particles with the core material adhered thereto. The base material with the core material attached thereto was added to 500 parts by weight of distilled water and dispersed to obtain a suspension A. [

A plating solution was prepared by adjusting a mixed solution of 500 g / L of nickel sulfate, 150 g / L of sodium hypophosphite, 150 g / L of sodium citrate and 6 mL / L of plating stabilizer to pH 8.0 as an electroplating nickel plating solution. 150 mL of this plating solution was added dropwise to the suspension A through a metering pump at an addition rate of 20 mL / min. The reaction temperature was set at 50 占 폚. Thereafter, stirring was continued until the pH became stable, confirming that the foaming of hydrogen stopped, and electroless plating electrical process was performed to obtain suspension B.

Subsequently, a plating solution was prepared in which a mixed solution of 500 g / L of nickel sulfate, 80 g / L of dimethylamine borane and 10 g / L of sodium tungstate was adjusted to pH 11.0 with sodium hydroxide as a nickel plating solution for a later process. 350 mL of this plating solution was added dropwise to the suspension B through a metering pump at an addition rate of 10 mL / min. The reaction temperature was set at 30 占 폚. Thereafter, the mixture was stirred until the pH became stable, confirming that the foaming of hydrogen stopped, and the electroless plating late process was carried out to obtain a suspension C.

Thereafter, the suspension C was filtered to take out the particles, washed with water and dried to obtain conductive particles having a nickel conductive layer disposed on the surface of the resin particles.

Preparation of anisotropic conductive film:

30 parts by weight of a phenoxy compound ("PKHC" manufactured by Inchem Co., Ltd.) as a thermosetting compound was added to a mixed solvent of 35 parts by weight of PGMEA and 35 parts by weight of methyl ethyl ketone and stirred at room temperature for 24 hours to obtain a 30 wt% dispersion of the phenoxy compound . Subsequently, 30 parts by weight of the above dispersion, 30 parts by weight of an epoxy compound (EPICLON HP-4032D, manufactured by DIC), 30 parts by weight of a microcapsule curing agent (Nova Cure HXA3922 manufactured by Asahi Kasei Corporation) , And 1 part by weight of a silane coupling agent ("KBM-403" manufactured by Shinetsu Chemical Industry Co., Ltd.) were added, and the conductive particles were further added in an amount of 10% by weight in 100% by weight of the conductive film After that, methyl ethyl ketone was further added so that the solid content became 50%, and the mixture was stirred at 2000 rpm for 5 minutes using a planetary stirrer to obtain a conductive paste. The obtained conductive paste was applied on the peeled polyethylene terephthalate and the solvent was dried to obtain an anisotropic conductive film having a thickness of 20 mu m.

Fabrication of first connection structure:

An electrode pattern with L / S of 20 占 퐉 / 20 占 퐉 (a composite electrode in which a TiO electrode portion having a thickness of 0.35 占 퐉, a TiAl electrode portion having a thickness of 1.0 占 퐉, and an IZO electrode portion having a thickness of 0.1 占 퐉 are stacked in this order) Was prepared. Further, a semiconductor chip having a gold electrode pattern (gold electrode thickness of 20 mu m) having L / S of 20 mu m / 20 mu m on the bottom was prepared.

An anisotropic conductive film was disposed on the upper surface of the glass substrate to form an anisotropic conductive film layer. Then, the semiconductor chip was laminated on the upper surface of the anisotropic conductive film layer such that the electrodes were opposed to each other. Thereafter, while the temperature of the head was adjusted so that the temperature of the anisotropic conductive film layer was 130 占 폚, a pressure heating head was placed on the upper surface of the semiconductor chip, and a pressure of 70 MPa was applied to the total area of the connection portion of the bump electrodes, .

Fabrication of second connection structure:

(A Mo electrode portion having a thickness of 0.3 占 퐉, an Al-Nd electrode portion having a thickness of 1.0 占 퐉 and an ITO electrode portion having a thickness of 0.1 占 퐉 in the direction from the inner surface to the outer surface of the electrode pattern having L / S of 20 占 퐉 / A composite electrode laminated in this order) on the upper surface was prepared. Further, a semiconductor chip having a gold electrode pattern (gold electrode thickness of 20 mu m) having L / S of 20 mu m / 20 mu m on the bottom was prepared.

An anisotropic conductive film was disposed on the upper surface of the glass substrate to form an anisotropic conductive film layer. Then, the semiconductor chip was laminated on the upper surface of the anisotropic conductive film layer such that the electrodes were opposed to each other. Thereafter, while the temperature of the head was adjusted so that the temperature of the anisotropic conductive film layer became 130 占 폚, a pressure heating head was placed on the upper surface of the semiconductor chip, and a pressure of 70 MPa was applied to the connection area of the bump electrodes, .

(Example 2)

Conductive particles were obtained in the same manner as in Example 1 except that 1 g of the metallic nickel particle slurry (average particle diameter 100 nm) was changed to 0.8 g of an alumina particle slurry (average particle diameter 100 nm). Anisotropic conductive films and first and second connection structures were obtained in the same manner as in Example 1 except that the obtained conductive particles were used.

(Example 3)

300 g of 0.13 wt% aqueous ammonia solution was placed in a 500 mL reaction vessel equipped with a stirrer and a thermometer. Then, 3.8 g of methyltrimethoxysilane, 10.8 g of vinyltrimethoxysilane, 0.2 g of a silicone alkoxy oligomer A ("X-41-1053" manufactured by Shin-Etsu Chemical Co., Ltd., And a weight average molecular weight having an ethoxy group, an epoxy group and an alkyl group directly bonded to a silicon atom: about 1600) was added slowly. After the hydrolysis and condensation reaction proceeded with stirring, 1.6 mL of a 25% by weight aqueous ammonia solution was added, and the particles were isolated in an aqueous ammonia solution. The particles thus obtained were subjected to an oxygen partial pressure of 10 ^-10 atm at 450 DEG C And fired for 2 hours (firing time) to obtain organic-inorganic hybrid particles (base particles). The obtained organic-inorganic hybrid particles had a particle diameter of 3.00 mu m.

Conductive particles were obtained in the same manner as in Example 1 except that the base particles were changed to the above-mentioned organic-inorganic hybrid particles. Anisotropic conductive films and first and second connection structures were obtained in the same manner as in Example 1 except that the obtained conductive particles were used.

(Example 4)

In a 1000 mL separable flask equipped with a four-neck separable cover, a stirrer, a three-way cock, a cooling tube and a temperature probe, 100 mmol of methyl methacrylate and 100 mmol of N, N, N-trimethyl- A monomer composition containing 1 mmol of ethylammonium chloride and 1 mmol of 2,2'-azobis (2-amidinopropane) dihydrochloride was weighed in ion-exchanged water to a solid content of 5% by weight, stirred at 200 rpm, Polymerization was carried out at 70 占 폚 in a nitrogen atmosphere for 24 hours. After completion of the reaction, the resultant was lyophilized to obtain insulating particles having an ammonium group on the surface and having an average particle diameter of 220 nm and a CV value of 10%. The insulating particles were dispersed in ion-exchanged water under ultrasonic irradiation to obtain a 10 wt% aqueous dispersion of insulating particles.

10 g of the conductive particles obtained in Example 1 were dispersed in 500 ml of ion-exchanged water, 4 g of an aqueous dispersion of insulating particles was added, and the mixture was stirred at room temperature for 6 hours. Filtered through a mesh filter of 0.3 mu m, washed with methanol, and dried to obtain conductive particles having insulating particles adhered thereto.

As a result of observation by a scanning electron microscope (SEM), only one coating layer composed of insulating particles was formed on the surface of the conductive particles. The coated area of the insulating particles (i.e., the projected area of the particle diameter of the insulating particles) with respect to the area of 2.5 mu m from the center of the conductive particles was calculated by image analysis, and the covering ratio was found to be 50%.

Anisotropic conductive films and first and second connection structures were obtained in the same manner as in Example 1 except that the obtained conductive particles were used.

(Example 5)

Conductive particles were obtained in the same manner as in Example 1 except that divinylbenzene copolymer resin particles having a particle diameter of 2.0 占 퐉 were used as base particles. Anisotropic conductive films and first and second connection structures were obtained in the same manner as in Example 1 except that the obtained conductive particles were used.

(Example 6)

Divinylbenzene copolymer resin particles (Micropearl SP-203, manufactured by Sekisui Chemical Co., Ltd.) having a particle size of 3.0 占 퐉 were prepared. 10 parts by weight of the resin particles were dispersed in 100 parts by weight (100 g) of an alkali solution containing 5% by weight of a palladium catalyst solution by using an ultrasonic disperser, and the solution was filtered to take out the resin particles. Subsequently, the resin particles were added to 100 parts by weight of a 1 wt% solution of dimethylamine borane to activate the surface of the resin particles. The surface-activated resin particles were sufficiently washed with water and then added to 500 parts by weight of distilled water and dispersed to obtain a suspension D.

A plating solution prepared by adjusting a mixture of 500 g / L of nickel sulfate, 150 g / L of sodium hypophosphite, 150 g / L of sodium citrate and 6 mL / L of plating stabilizer was adjusted to 8.0 with ammonia as an electrolytic nickel plating solution. 150 mL of this plating solution was added dropwise to the suspension D through a metering pump at an addition rate of 20 mL / min. The reaction temperature was set at 50 占 폚. Thereafter, stirring was continued until the pH became stable, confirming that the foaming of hydrogen stopped, and electroless plating electrical process was performed to obtain a suspension E.

Subsequently, a plating solution was prepared in which a mixed solution of 500 g / L of nickel sulfate, 80 g / L of dimethylamine borane and 10 g / L of sodium tungstate was adjusted to pH 11.0 with sodium hydroxide as a nickel plating solution for a later process.

1 g of a metallic nickel particle slurry (average particle diameter 100 nm) was added to the suspension E for 3 minutes, and then 350 mL of a nickel plating solution for a later process was added dropwise to the suspension E through a metering pump at an addition rate of 10 mL / min. The reaction temperature was set at 30 占 폚. Thereafter, stirring was continued until the pH became stable, confirming that the foaming of hydrogen stopped, and a later-stage electroless plating step was carried out to obtain a suspension F.

Thereafter, by filtering the suspension F, the particles were taken out, washed with water and dried to obtain conductive particles having a nickel conductive layer disposed on the surface of the resin particles.

Anisotropic conductive films and first and second connection structures were obtained in the same manner as in Example 1 except that the obtained conductive particles were used.

(Example 7)

Polystyrene particles having an average particle diameter of 0.85 占 퐉 were prepared as seed particles. 3.0 g of the polystyrene particles, 500 g of ion-exchanged water, and 120 g of a 5 wt% aqueous solution of polyvinyl alcohol were mixed and dispersed by ultrasonic waves, and the resulting mixture was added to a separable flask and stirred uniformly. As internal forming materials, 49 g of cyclohexyl methacrylate, 1.5 g of 2,2'-azobis (methyl isobutyrate) ("V-601" manufactured by Wako Pure Chemical Industries, Ltd.) as the organic compound A, 3.0 g of triethanolamine and 40 g of ethanol were added to 400 g of ion-exchanged water to prepare Emulsion A. The above emulsion A was further added to the separable flask to which the polystyrene particles as the seed particles were added and stirred for 4 hours to absorb the organic compound A into the seed particles, A suspension was obtained. Subsequently, 49 g of divinylbenzene (purity: 96 wt%) as organic compound B, 1.5 g of benzoyl peroxide (niche BW), 3.0 g of triethanolamine laurylsulfate, 40 g of ethanol Was added to 400 g of ion-exchanged water to prepare Emulsion B. The emulsion B was further added to the separable flask containing the suspension and stirred for 4 hours to absorb the organic compound B into the seed particles in which the internal forming material swelled.

Thereafter, 360 g of a 5 wt% aqueous solution of polyvinyl alcohol was added and heating was started. The reaction was conducted at 75 캜 for 5 hours and then at 85 캜 for 6 hours to obtain a base particle A having an average particle diameter of 3 탆. 10 parts by weight of the base particle A was dispersed in 100 parts by weight of an alkali solution containing 5% by weight of a palladium catalyst solution by using an ultrasonic dispersing machine, and then the solution was filtered to take out the base particle A. Subsequently, the base particle A was added to 100 parts by weight of a 1 wt% solution of dimethylamine borane to activate the surface of the base particle A. The surface-activated base particle A was thoroughly washed with water and then added to 500 parts by weight of distilled water and dispersed to obtain a dispersion. Subsequently, 1 g of a nickel particle slurry (average particle diameter 100 nm) was added for 3 minutes to the dispersion to obtain a suspension containing the base material to which the core material was adhered.

Conductive particles were obtained in the same manner as in Example 1 except that the suspension obtained above was used in place of the suspension A. [

Anisotropic conductive films and first and second connection structures were obtained in the same manner as in Example 1 except that the obtained conductive particles were used.

(Example 8)

The same suspension A as in Example 1 was prepared.

A first nickel plating solution (pH 7.0) containing 0.12 mol / L of nickel sulfate, 0.50 mol / L of dimethylamine borane and 0.25 mol / L of sodium citrate was prepared.

A second nickel plating solution (pH 10.0) containing 0.12 mol / L of nickel sulfate, 2.00 mol / L of hydrazinium sulfate and 0.25 mol / L of glycine was prepared

The first nickel plating solution (pH 7.0) was gradually added dropwise to the suspension A while agitating the obtained suspension A at 50 占 폚 and electroless nickel-boron plating was carried out to form a nickel-boron conductive layer (boron content 2.0% by weight). The suspension was stirred until the pH of the suspension became stable, confirming that the foaming of hydrogen stopped, and a suspension H after electroless nickel-boron plating was obtained.

Thereafter, the suspension H was filtered to take out the particles and washed with water to obtain particles having a first conductive portion (thickness: 86 nm) formed on the surface of the base particles. The particles were thoroughly washed with water and then added to 500 parts by weight of distilled water and dispersed to obtain a suspension I.

The second nickel plating solution (pH 10.0) was gradually added dropwise while stirring the obtained suspension I at 80 占 폚 and electroless pure nickel plating was carried out to form a nickel conductive layer (phosphorus content: 0%) as an outer second conductive portion . By filtering the suspension, the particles were taken out, washed with water, and then stirred until the pH became stable to confirm that the foaming of hydrogen stopped, and a suspension J after electroless pure nickel plating was obtained.

Thereafter, the suspension J was filtered to take out the particles, washed with water and dried to obtain conductive particles having a conductive portion (thickness 49 nm) of the second high purity Ni disposed on the outer surface of the first conductive portion.

Anisotropic conductive films and first and second connection structures were obtained in the same manner as in Example 1 except that the obtained conductive particles were used.

(Comparative Example 1)

Conductive particles were obtained in the same manner as in Example 1 except that 1 g of the metallic nickel particle slurry (average particle diameter 100 nm) was not used and no protrusion was formed on the surface of the conductive particles. Anisotropic conductive films and first and second connection structures were obtained in the same manner as in Example 1 except that the obtained conductive particles were used.

(Comparative Example 2)

Conductive particles were obtained in the same manner as in Example 1 except that the resin particles as the copolymer of polytetramethylene glycol diacrylate and divinylbenzene were used as the base particles. Anisotropic conductive films and first and second connection structures were obtained in the same manner as in Example 1 except that the obtained conductive particles were used.

(evaluation)

(1) Compressive modulus (10% K value) when conductive particles were compressed by 10%

The compression elastic modulus (10% K value) of the obtained conductive particles was measured by the above-described method using a micro compression tester (Fisher Scope H-100 manufactured by Fisher Company).

(2) Viscosity of binder resin

Using the obtained conductive film (anisotropic conductive film), the viscosity of the binder resin at 130 占 폚 was measured using a viscoelasticity measuring device ("AR-2000ex" manufactured by TA Instruments).

(3) the state of indentation

Using a differential interference microscope ("BH3-MJL liquid crystal panel inspection microscope" manufactured by Olympus Co., Ltd.), the electrode provided on the glass substrate was observed on the glass substrate side of the obtained first and second connection structures, , The number of indentations having a depth of 5 nm or more per 500 mu m ² surface area was measured.

(4) CV value

Using a differential interference microscope ("BH3-MJL liquid crystal panel inspection microscope" manufactured by Olympus Corporation), the electrodes provided on the glass substrate on the glass substrate side of the obtained first and second connection structures were observed. The number of the conductive particles arranged at a surface area of 500 mu m < ² > of the electrode was measured at 100 places. The CV value of the number of the conductive particles in the measurement value at 100 points was determined.

(5) Initial connection resistance A

Measurement of connection resistance:

The connection resistance A between the opposing electrodes of the obtained first and second connection structures was measured by the four-terminal method. In addition, the initial connection resistance A was determined based on the following criteria. The connection resistance A is preferably 10 Ω or less, more preferably 5.0 Ω or less, more preferably 3.0 Ω or less, and particularly preferably 1.5 Ω or less.

[Evaluation Criteria of Initial Connection Resistance A]

○ ○ ○: Connection resistance A is less than 1.0Ω

○○: Connection resistance A exceeds 1.0Ω, and 1.5Ω or less

?: Connection resistance A exceeding 1.5?, 3.0?

?: Connection resistance A exceeding 3.0?, Not more than 5.0?

X: Connection resistance A exceeds 5.0 Ω

The results are shown in Tables 1 and 2 below. In the column of "change in hardness of the base particles" in Table 1, "A" indicates that the outside hardness of the base particles is not harder than that of the inside, "B" indicates that the outside hardness of the base particles is harder than the inside, .

When the viscosity of the binder resin at 130 ° C is not 100 Pa · s, the conductive particles are mixed with the binder resin having a viscosity of 100 Pa · s at 130 ° C so that the content of the conductive particles is 30,000 ± 2500 / The evaluations of (3), (4) and (5) were the same for the conductive film (anisotropic conductive film) .

One… Conductive particle
2… Base particles
3 ... Conductive part
11 ... Conductive particle
11a ... spin
12 ... Conductive part
12a ... spin
13 ... Core material
14 ... Insulating material
21 ... Conductive particle
21a ... spin
22 ... Conductive part
22a ... spin
22A ... The first conductive portion
22Aa ... spin
22B ... The second conductive portion
22Ba ... spin
51 ... Connection structure
52 ... The first connection object member
52a ... The first electrode
53 ... The second connection object member
53a ... The second electrode
54 ... Connection

Claims (12)

A first connection member having a first electrode on a surface thereof and a binder resin having a viscosity of not less than 50 Pa · s and not more than 1000 Pa · s at 130 ° C. and a conductive film containing conductive particles are used, And the conductive film is disposed between the first connection target member and the second connection target member so that the first electrode and the second electrode face each other to obtain a laminated body The process,
And a step of heating and pressing the laminate and thermocompression bonding to obtain a connection structure,
Wherein the number of indentations having a depth of 5 nm or more at which the conductive particles are pressed into the first electrode is 5 or more per 500 m ² of the surface area of the first electrode. The method of manufacturing a connection structure according to claim 1, wherein the first electrode comprises Ti or Al and has a thickness of 1 占 퐉 or more and 2 占 퐉 or less. The plasma display panel according to claim 1, wherein the first electrode has a TiO 2 electrode portion having a thickness of 0.1 μm or more and 0.5 μm or less, an AlTi electrode portion having a thickness of 0.5 μm or more and 2.0 μm or less, The IZO electrode portion having a thickness of not more than 0.1 mu m and not more than 0.5 mu m in thickness and the second electrode having a thickness of not less than 0.5 mu m and not more than 2.0 mu m And an ITO electrode portion having a thickness of 0.05 占 퐉 or more and 0.2 占 퐉 or less are laminated in this order. 4. The plasma display panel according to claim 3, wherein the first electrode has a TiO2 electrode portion having a thickness of 0.1 占 퐉 or more and 0.5 占 퐉 or less, an AlTi electrode portion having a thickness of 0.5 占 퐉 or more and 2.0 占 퐉 or less, And an IZO electrode portion having a thickness of 탆 or less are laminated in this order. The piezoelectric device according to claim 3, wherein the first electrode has a Mo electrode portion having a thickness of 0.1 占 퐉 or more and 0.5 占 퐉 or less, an Al-Nd electrode portion having a thickness of 0.5 占 퐉 or more and 2.0 占 퐉 or less, And an ITO electrode portion having a thickness of at most 0.2 mu m is laminated in this order. The method for manufacturing a connection structure according to any one of claims 1 to 5, wherein the connection structure between the first electrode and the second electrode is 1.5 Ω or less. Conductive particles which are blended in a binder resin and used for obtaining a conductive film,
The conductive particles used were a binder resin having a viscosity of 110 ± 10 Pa · s at 130 ° C. and a conductive film containing the conductive particles at a content of 30000 ± 2500 particles / A first connection target member having a bump electrode having a thickness of 1 占 퐉 or more and 2 占 퐉 or less and having a thickness of 1 占 퐉 or more and 2 占 퐉 or less is used and a second connection object member having an Au bump electrode as a second electrode is used, The conductive film is disposed between the first connection object member and the second connection object member so that the first bump electrode and the second bump electrode face each other and the conductive film is formed at a temperature of 130 占 폚 and a total area The number of indentations having a depth of 5 nm or more at which the conductive particles are press-fitted into the first electrode in the obtained connection structure obtained by thermocompression bonding with pressure for 10 seconds to obtain a connection structure, Wherein the conductive particles exhibit a value of 5 or more per ² mu m. 8. The conductive particle according to claim 7, wherein the conductive particles are the conductive particles which are blended in a binder resin having a viscosity at 130 DEG C of not less than 50 Pa · s and not more than 1000 Pa · s to obtain a conductive film. A binder resin having a viscosity at 130 占 폚 of 50 Pa · s or more and 1000 Pa · s or less,
A conductive film comprising the conductive particles according to claim 7 or 8. A first connection target member having a first electrode on its surface,
A second connection target member having a second electrode on its surface,
And a connecting portion connecting the first connection target member and the second connection target member,
Wherein the material of the connecting portion is the conductive film according to claim 9,
Wherein the first electrode and the second electrode are electrically connected by the conductive particles. The connection structure according to claim 10, wherein the connection resistance between the first electrode and the second electrode is 1.5 Ω or less. A binder resin having a viscosity at 130 DEG C of not less than 50 Pa · s and not more than 1000 Pa · s, and conductive particles,
Wherein the conductive film comprises a first connection target member having a bump electrode having a thickness of 1 占 퐉 or more and 2 占 퐉 or less and containing Ti or Al as a first electrode and an Au bump electrode as a second electrode on the surface And the conductive film is disposed between the first connection target member and the second connection target member so that the first electrode and the second electrode face each other, The number of indentations having a depth of 5 nm or more at which the conductive particles are press-fitted into the first electrode in the obtained connection structure when the connection structure is obtained by thermocompression bonding at a pressure of 70 MPa per a total area of the connecting portions of the electrodes for 10 seconds, Wherein the conductive film exhibits a value of 5 or more per 500 mu m ² of the surface area of the electrode.

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