WO2008026517A1 - Conductive bonding material and electronic device - Google Patents
Conductive bonding material and electronic device Download PDFInfo
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- WO2008026517A1 WO2008026517A1 PCT/JP2007/066475 JP2007066475W WO2008026517A1 WO 2008026517 A1 WO2008026517 A1 WO 2008026517A1 JP 2007066475 W JP2007066475 W JP 2007066475W WO 2008026517 A1 WO2008026517 A1 WO 2008026517A1
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- metal powder
- melting point
- powder
- bonding material
- conductive bonding
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Classifications
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/30—Assembling printed circuits with electric components, e.g. with resistors
- H05K3/32—Assembling printed circuits with electric components, e.g. with resistors electrically connecting electric components or wires to printed circuits
- H05K3/321—Assembling printed circuits with electric components, e.g. with resistors electrically connecting electric components or wires to printed circuits by conductive adhesives
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
- C09J9/02—Electrically-conducting adhesives
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
- H05K2201/0203—Fillers and particles
- H05K2201/0263—Details about a collection of particles
- H05K2201/0272—Mixed conductive particles, i.e. using different conductive particles, e.g. differing in shape
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/10—Details of components or other objects attached to or integrated in a printed circuit board
- H05K2201/10613—Details of electrical connections of non-printed components, e.g. special leads
- H05K2201/10621—Components characterised by their electrical contacts
- H05K2201/10636—Leadless chip, e.g. chip capacitor or resistor
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/04—Soldering or other types of metallurgic bonding
- H05K2203/0425—Solder powder or solder coated metal powder
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
- Y10T428/2852—Adhesive compositions
- Y10T428/2857—Adhesive compositions including metal or compound thereof or natural rubber
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31678—Of metal
Definitions
- the present invention relates to a conductive bonding material and an electronic device, and more specifically, a conductive bonding material for bonding electric structures such as a chip-type electronic component and a printed wiring board, and a plurality of electric structures including the conductive structure.
- the present invention relates to an electronic device bonded through a conductive bonding material.
- the first electrode 102 is formed on the substrate 101
- the second electrode 104 is formed on the electronic device 103
- the first electrode 102 is formed.
- the second electrode 104 is connected to an electrode connecting portion 105 in which conduction is ensured by fusion of metal fine particles, and an intermediate connecting portion 106 made of a conductive adhesive is interposed between the electrode connecting portions 105.
- the fine metal particles are fused at a temperature lower than the heat curing temperature of the conductive adhesive, and the conductive adhesive is not fused at a temperature lower than the heat curing temperature of the conductive adhesive!
- a connection structure containing a filler has been proposed!
- the electrode connecting portion 105 is fused with metal fine particles such as Ag that cause fusion at a temperature lower than the heat curing temperature of the conductive adhesive, and at a temperature lower than the heat curing temperature of the conductive adhesive. It is comprised with the conductive adhesive which consists of an electroconductive filler with a particle size which is not, and an adhesive agent.
- Patent Document 1 the first and second electrodes 102 and 104 and the conductive filler are fused through the metal fine particles contained in the electrode connecting portion 105 by heat curing, The conductive fillers are fused with each other through the metal fine particles, thereby improving the adhesion at the interface.
- Patent Document 2 proposes a thermally conductive joined body in which a first substrate 107 and a second substrate 108 are joined with a thermally conductive material 109, as shown in FIG. .
- the heat conductive material 109 of Patent Document 2 includes a thermosetting resin 110 containing an organic acid and a heat conductive filler, and the heat conductive filler is a thermosetting temperature of the thermosetting resin 110.
- a heat conductive material comprising V, a first filler 111 having a melting point, and a second filler 112 having a melting point lower than that of the thermosetting resin 110.
- Patent Document 2 includes the second filler 112 having a melting point that is lower than the thermosetting temperature of the thermosetting resin 110, which is one of the heat conductive fillers. Therefore, the thermosetting resin 110 is cured. Before the second filler 112 is melted, the first filler 111 and the second filler 112 are fused. In addition, since the first filler 111 having a melting point higher than the thermosetting temperature of the thermosetting resin is included, the first filler 111 remains after the thermosetting resin 110 is cured. The form can be maintained, thereby suppressing an increase in thermal resistance.
- the heat conductive material includes the thermosetting resin 110 and the heat conductive filler, the bonding temperature can be lowered, and since the resin-based material is used as a base, the elastic modulus is lowered and the thermal stress is reduced. Is possible. In this way, we are trying to obtain a thermally conductive material with high thermal conductivity and good connection reliability.
- Patent Document 1 JP 2005-93826 A (Claim 1, Claim 6)
- Patent Document 2 Japanese Patent Application Laid-Open No. 2004-335872 (Claim 1, paragraph number [0040], etc.).
- the electrode connection portion 105 is electrically connected to the intermediate connection portion 1 although the metal fine particles that melt at or below the heat curing temperature of the conductive adhesive are fused.
- Pb-free solder due to environmental considerations, etc.
- This Pb-free solder has a melting temperature of 270 ° C to 280 ° C. The high temperature and thus the hardened metal remelts and is more susceptible to debonding at the joint interface.
- Patent Document 2 no consideration is given to the content of the heat conductive filler and the particle sizes of the first and second fillers. That is, depending on the content of these heat conductive fillers and the particle sizes of the first and second fillers, there is a risk that the adhesion strength to the bonded surfaces after heat curing may be reduced, and high temperature and high humidity. If exposed underneath for a long time, the connection resistance may increase, leading to a decrease in conductivity.
- the present invention has been made in view of such circumstances. Even when the reflow heat treatment is repeated or a thermal shock accompanied by a rapid temperature change is applied, good electrical conductivity and high V It is an object to provide a conductive bonding material having connection strength and an electronic device using the same.
- the conductive bonding material according to the present invention includes a thermosetting resin, a first metal powder that melts at a temperature not higher than the thermosetting temperature of the thermosetting resin, and the heat Does not melt at a temperature lower than the thermosetting temperature of the curable resin, and reacts with the first metal powder during the heat curing of the thermosetting resin to produce a reactant having a high melting point of 300 ° C or higher.
- the particle size ratio D1 / D2 between the average particle diameter D1 of the first metal powder and the average particle diameter D2 of the second metal powder is 75 to 88% by weight in total. 6. Characterized by zero
- the volume ratio of the first metal powder to the total amount of the first metal powder and the second metal powder is 25 to 75% by volume. Special It is a sign.
- the second metal powder has higher wettability to the first metal powder than the second metal powder, and the thermosetting property. It is characterized by being coated with a low melting point metal that melts at a temperature lower than the thermosetting temperature of the resin, and the low melting point metal is characterized by being a metal containing Sn.
- the second metal powder is coated with a metal having higher wettability with respect to the first metal powder than the second metal powder. It is also preferable that the metal having high wettability is a noble metal.
- the conductive bonding material of the present invention is characterized in that the first metal powder is a Sn-Bi alloy powder.
- an electronic device is an electronic device including a first electric structure having a first electrode and a second electric structure having a second electrode, The first electrode and the second electrode are electrically connected via the conductive bonding material described above, and the interface between the first metal powder and the second metal powder, At least one of the interface between the first metal powder and the first electrode and the interface between the first metal powder and the second electrode has a high melting point of 300 ° C. or higher. It is characterized by being bound by reactants.
- thermosetting resin and the first metal powder that melts at a temperature lower than the thermosetting temperature of the thermosetting resin.
- a reaction product that does not melt at a temperature lower than or equal to the thermosetting temperature of the thermosetting resin and has a high melting point of 300 ° C. or more by reacting with the first metal powder during the heat curing of the thermosetting resin.
- a second metal powder to be produced (for example, Cu powder) and a reducing substance that removes oxides formed on the surface of the second metal powder, and the first metal powder and the first metal powder
- the total content of the metal powder 2 is 75 to 88% by weight, and the particle diameter ratio D1 between the average particle diameter D1 of the first metal powder and the average particle diameter D2 of the second metal powder Since / D2 is 0.5 to 6.0, the first metal powder wets and spreads during heating and curing, and the second metal powder Connected to form a conductive path.
- the first metal powder then reacts with the second metal powder to produce a high melting point reactant that does not melt at 300 ° C. In this way, it is possible to obtain a conductive bonding material with excellent connection reliability and excellent connection reliability having a strong adhesive force.
- the first metal powder contains Bi that has a small volume expansion at the time of melting, such as Sn-Bi alloy powder, even if the first metal powder is changed to the second metal powder. Even when the high-melting-point reactant is not sufficiently formed due to insufficient wetting and spreading of the material, it is possible to secure a good fixing strength that is unlikely to cause damage to the bonding interface due to volume expansion during melting.
- the volume ratio of the first metal powder to the total amount of the first metal powder and the second metal powder is 25 to 75% by volume, the volume occupied by the first metal powder The ratio is maintained within an appropriate range, and a large number of conductive paths can be easily formed. That is, the shortage of the first metal powder or the remaining of the unreacted first metal powder that did not react with the second metal powder is suppressed, and the desired electrical conductivity and connection reliability are achieved. A conductive bonding material that can be secured can be obtained.
- the second metal powder has higher wettability with respect to the first metal powder than the second metal powder and is equal to or lower than the thermosetting temperature of the thermosetting resin. Since it is coated with a low melting point metal (for example, Sn) that melts at 1! /, The first metal powder easily wets and spreads on the surface of the second metal powder during thermosetting of the thermosetting resin. As a result, the generation of a high melting point reactant having a melting point of 300 ° C or higher can be promoted, a conductive path having better conductivity can be formed, and the bonding strength of the bonding interface can be further improved.
- Sn low melting point metal
- the second metal powder may be coated with a metal (for example, a noble metal such as Au) having higher wettability with respect to the first metal powder than the second metal powder.
- a metal for example, a noble metal such as Au
- the first electrode of the first electric structure and the second electrode of the second electric structure are electrically connected via the conductive bonding material described above. Together with the interface between the first metal powder and the second metal powder, the interface between the first metal powder and the first electrode, and the first metal powder. Of the interface with the second electrode Since at least one interface is bonded with a high melting point reactant having a high melting point of 300 ° C. or higher, a conductive path having good conductivity is formed, and these bonding interfaces are fixed with the high melting point reactant.
- FIG. 1 is a schematic cross-sectional view showing an embodiment of an electronic device manufactured using a conductive bonding material according to the present invention.
- FIG. 2 is an enlarged view of part A before heat curing in FIG.
- FIG. 3 is an enlarged view of part A after heat curing in FIG.
- FIG. 4 is a cross-sectional view schematically showing a cured state of the conductive bonding material when the average particle size of the low melting point metal is excessively smaller than the average particle size of the high melting point metal.
- FIG. 5 is a cross-sectional view schematically showing a cured state of the conductive bonding material when the average particle size of the low melting point metal is excessively larger than the average particle size of the high melting point metal.
- FIG. 6 is a schematic diagram of a connection structure described in Patent Document 1.
- FIG. 7 is a schematic view showing a state before curing of the thermally conductive joined body described in Patent Document 2.
- FIG. 1 is a cross-sectional view schematically showing one embodiment of an electronic device manufactured using the conductive bonding material of the present invention.
- the present electronic device has a chip-type electronic device such as a ceramic capacitor on a substrate (first electrical structure) 2 such as a printed wiring board on which land electrodes (first electrodes) la and lb are formed.
- first electrical structure such as a printed wiring board on which land electrodes (first electrodes) la and lb are formed.
- second electrical structure) 3 is installed!
- This chip-type electronic component 3 has external electrodes (second electrodes) 5a and 5b formed at both ends of an electronic component main body 4 whose main component is a ceramic material, and the external electrodes 5a and 5b and the land Electrode la
- And lb are electrically connected by conductive bonding materials 6a and 6b.
- FIG. 2 is an enlarged view of a portion A before the heat curing in FIG.
- the conductive bonding material 6a includes a thermosetting resin 7 having a thermosetting temperature of about 200 ° C, for example, and a low-melting-point metal powder that melts at a temperature lower than the thermosetting temperature of the thermosetting resin 7 (first 8 and the thermosetting resin 7 does not melt at a temperature equal to or lower than the thermosetting temperature of the thermosetting resin 7, and reacts with the low melting metal powder 8 when the thermosetting resin 7 is heated and cured, so that the melting point is 300 °.
- a refractory metal powder (second metal powder) 9 that generates a high melting point reactant of C or higher, and a reducing substance (not shown) that removes oxides formed on the surface of the refractory metal powder 9 Contains
- the conductive bonding material 6a has a low melting point metal powder 8, a high melting point metal powder 9, and a reducing substance (not shown) dispersed in a thermosetting resin 7.
- the above-mentioned reactant is a high-melting-point reactant having a melting point of 300 ° C or higher generated by the reaction between the low-melting-point metal powder and the high-melting-point metal powder as described above. Inter compound or solid solution.
- FIG. 3 is an enlarged view of part A after the heat curing of FIG.
- the conductive bonding material 6a is applied to the external electrode 5a and the land electrode la and heat-treated at a temperature equal to or higher than the thermosetting temperature, the low melting metal powder 8 is melted and spreads.
- the high melting point metal powders 9 and 9 are connected via the low melting point metal powder 8 to generate a large number of conductive paths 11. Is done.
- the refractory metal powder 9 does not melt at the thermosetting temperature of the thermosetting resin 7! /. Therefore, even if only the refractory metal powder 9 is dispersed in the thermosetting resin 7, Generating pass 11 is difficult.
- the low melting point metal powder 8 that melts at a temperature lower than the thermosetting temperature of the thermosetting resin 7 is dispersed in the thermosetting resin 7, so that the heat curing temperature is higher than the thermosetting temperature.
- the low melting point metal powder 8 is melted and spread.
- the high melting point metal powders 9 and 9 are connected by the low melting point metal powder 8, and a large number of conductive paths 11 having good conductivity are generated.
- this low melting point metal powder 8 reacts with the high melting point metal powder 9 to produce a high melting point reaction product having a melting point of 300 ° C or higher, reflow heat treatment using Pb-free solder or heat Even when it is exposed to high temperatures and humidity for a long time, such as repeated impacts, the metal at the bonding interface will not remelt, and it will be possible to obtain an electronic device with good bonding strength. .
- the molten low melting point metal powder also wets and spreads on the land electrodes la and lb and the external electrodes 5a and 5b. Therefore, the Ag—Pd contained in the land electrodes la and lb and the external electrodes 5a and 5b.
- a high-melting point reaction product is also formed with metals such as Sn and Sn, and a conductive path 11 is formed. Therefore, this also makes it possible to obtain an electronic device having a stronger adhering force between the land electrodes la and lb and the external electrodes 5a and 5b and an excellent mechanical strength.
- the conductive bonding material contains a reducing substance, whereby the oxide generated on the surface of the refractory metal powder 9 can be removed. That is, by removing the oxide generated on the surface, the low melting point metal powder 8 tends to wet and spread on the surface of the high melting point metal powder 9 when the thermosetting resin 7 is heated and cured, and the conductivity is higher. A conductive path 11 is formed and the formation of a high melting point reactant can be promoted. Therefore, according to this, it is possible to obtain an electronic device having a much stronger fixing force between the land electrodes la and lb and the external electrodes 5a and 5b.
- a reducing substance for example, an organic acid such as succinic acid or acetic acid, hydrochloric acid, odorous acid or the like can be preferably used. of If so, substances other than acids can also be used.
- an electronic device in which the bonding interface between the land electrodes la and lb and the external electrodes 5a and 5b is bonded with a strong fixing force while ensuring good electrical conductivity. Obtain power S.
- the contents of the low melting point metal powder 8 and the high melting point metal powder 9 in the conductive bonding materials 6a and 6b that is, the total content of the metal powder is 75 to 88% by weight. It is set.
- the metal powder in the conductive bonding materials 6a and 6b is too small. Even if the low melting metal powder 8 wets and spreads, it is not connected to the high melting metal powder 9 and it becomes difficult to generate the conductive path 11, and a high melting point reactant having a melting point of 300 ° C or higher can be sufficiently generated. Can not be. As a result, the conductivity is lowered, and particularly when left in a high temperature and high humidity for a long time, the conductivity is reduced.
- the total content of the metal powder in the conductive bonding materials 6a and 6b exceeds 88% by weight, the content of the thermosetting resin 7 in the conductive bonding materials 6a and 6b becomes too small. In addition, the adhesion strength between the land electrodes la and lb and the external electrodes 5a and 5b may be reduced.
- the total content of the metal powder in the conductive bonding materials 6a and 6b is set to 75 to 88% by weight.
- the particle diameter ratio D1 / D2 between the average particle diameter D1 of the low melting point metal powder 8 and the average particle diameter D2 of the high melting point metal powder 9 is set to 0.5 to 6.0.
- the average particle size D1 of the low melting metal powder 8 relative to the average particle size D2 of the refractory metal powder 9 is too small.
- the interval between the high melting point metal powders 9 becomes wider than the average particle diameter D1 of the powder 8, and the low melting point metal powder 8 connects the high melting point metal powders 9 even after heat curing as shown in FIG. As a result, there is a portion where the conductive path 11 cannot be generated.
- the average particle size D2 of the refractory metal powder 9 The average particle diameter Dl of the low-melting-point metal powder 8 is too large, and the dispersion state of the low-melting-point metal powder 8 and the high-melting-point metal powder 9 in the conductive bonding material deteriorates. As shown in FIG. During melting, the low melting point metal powders 8 are easily fused. For this reason, the formation of the conductive path 11 connecting the refractory metal powders 9 becomes insufficient.
- the particle diameter ratio D1 / D2 between the average particle diameter D1 of the low melting point metal powder 8 and the average particle diameter D2 of the high melting point metal powder 9 is set to 0.5 to 6.0. It is set.
- thermosetting resin 7 it has good adhesiveness by heat curing treatment, and has sufficient fixing strength between the land electrodes la and lb and the external electrodes 5a and 5b.
- thermosetting resin 7 it is possible to use epoxy-based, phenol-based, and acrylic-based thermosetting resins, polyimide-based, polyurethane-based, melamine-based, and urea-based thermosetting resins that are not particularly limited.
- Epoxy-based The thermosetting resin is particularly preferably used.
- bisphenol monore F type bisphenol A type
- hydrogenated bisphenol type phenol nopolac type
- glycidylamine type glycidylamine type
- naphthalene type cyclopentagen type
- cyclohexane type hexanetetrahydroxyphenolethane type
- Hydantoin-type polyglycol-type
- ether-type epoxy resins and modified epoxy resins obtained by modifying these epoxy resins with silicone, rubber, urethane, chelate, etc.
- liquid epoxy type thermosetting resins such as bisphenol F type epoxy resin and bisphenol A type epoxy resin do not require an organic solvent to maintain workability. It is preferable from the viewpoint of work, and it is more preferable that when the thermosetting resin is heat-cured, the organic solvent is volatilized to form voids (voids) at the bonding interface.
- the low melting point metal powder 8 is not particularly limited as long as it does not melt at the thermosetting temperature of the thermosetting resin 7! /, Sn, In, Sn—Bi, Sn — Force that can use In, Sn—In—Bi, Sn—Pb, etc. It is preferable to use a Bi-based alloy that has a small volume expansion upon melting, such as Sn—Bi! /. Low volume expansion at the time of melting! / By using low melting point metal powder 8 containing Bi, it is excellent in that the joint interface is not easily damaged due to volume expansion. Fixing strength can be obtained.
- the high melting point metal powder 9 does not melt at a temperature lower than the thermosetting temperature of the thermosetting resin 7, and reacts with the low melting point metal powder 8 during the heat curing of the thermosetting resin 7. It is not particularly limited as long as it generates a high melting point reactant having a melting point of 300 ° C or higher.
- the low melting point metal powder 8 a Sn alloy such as Sn-Bi is used, and the high melting point metal powder is used.
- the Sn component force SCu contained in the low-melting-point metal powder 8 reacts during heat curing to produce intermetallic compounds such as Cu Sn and Cu Sn. Also low melting point
- intermetallic compounds are high melting point reactants having a melting point of 300 ° C. or higher, so that the joint interface is not affected even when repeated reflow heat treatment or repeated thermal shock with sudden temperature changes is applied. Use force S to ensure a strong adhesive force that does not remelt.
- the volume ratio of the low melting point metal powder 8 to the total amount of the metal powders (low melting point metal powder 8 and high melting point metal powder 9) is preferably 25 to 75% by volume.
- the volume ratio of the low melting point metal powder 8 is less than 25% by volume with respect to the total amount of the metal powder.
- the volume ratio of the low melting point metal powder 8 tends to be reduced and the formation of the conductive path 11 is hindered, leading to a decrease in conductivity, while the volume ratio of the low melting point metal powder 8 is less than that of the metal powder. If the total amount exceeds 75% by volume, it will not react with the refractory metal powder 9! /, Unreacted low-melting metal powder 8 will remain, leading to reduced continuity and reduced connection reliability at high temperatures. Because it becomes a tendency.
- the high melting point metal powder 9 it is also preferable to coat the high melting point metal powder 9 with a metal having higher wettability with respect to the low melting point metal powder 8 than the high melting point metal powder 9.
- the low melting point metal powder 8 can be used when the thermosetting resin 7 is heated and cured. Is easy to wet and spread on the surface of the refractory metal powder 9.
- Such high wettability metals include metals that melt below the thermosetting temperature of thermosetting resins such as Sn, Sn-Bi, Sn-In, Sn-Bi-In, Au, In consideration of the force capable of using noble metals such as Ag, Pt, Pd, the cost, the strength of the high melting point reactant, and durability, it is preferable to use Sn, Sn—In.
- thermosetting temperature of the thermosetting resin does not melt at the thermosetting temperature of the thermosetting resin, but melts at the thermosetting temperature of the thermosetting resin by reacting with the low melting point metal powder 8 Use metal seeds.
- Bisphenol F-type liquid epoxy resin as thermosetting resin, tertiary butyl daricidyl ether as reactive diluent, amine compound as curing agent, mixture of boron compound and epoxy resin as reaction inhibitor for the curing agent, reduction Succinic acid as a sexual substance
- Sn-58Bi powder (specific gravity: 8.93) (low melting point metal powder) having an average particle diameter D1 of lO ⁇ m and a melting point of 139 ° C was prepared, and the average particle diameter D2 was 5 m.
- Cu powder with a melting point of about 1080 ° C (Specific gravity: 8 ⁇ 75) (refractory metal powder) was prepared.
- the particle diameter ratio D1 / D2 between the average particle diameter D1 of Sn-58Bi powder and the average particle diameter D2 of Cu powder is 2.0.
- An Ag Pd paste was applied to a predetermined position on an alumina substrate having a thickness of 0.7 mm and baked to form a pair of land electrodes with an interval of 0.8 mm on the alumina substrate.
- the conductive bonding material was applied on the land electrode using a metal mask having a thickness of 50 am.
- a chip-type resistor component having an external electrode made of Sn and having a length of 1, 6 mm, a width of 0.8 mm, and a thickness of 0.8 mm was placed on the conductive bonding material, and the temperature was 200 °.
- Heat treatment was carried out in an air oven for 30 minutes under C! /, Sample numbers;! -6 samples were obtained.
- the initial value S of the fixing strength was measured using a series 4000).
- PCT pressure tapping force one test
- each of the samples Nos. 1 to 6 was subjected to reflow heat treatment by passing the sample 5 times through a reflow furnace adjusted to a maximum temperature of 270 ° C. Then, the resistance value R and the adhesion strength S after the reflow heat treatment are measured, and the resistance change rate AR after the reflow is based on the formula (2). Calculated.
- Table 1 shows the specifications and experimental results of the conductive bonding materials of sample numbers 1-6.
- connection resistance R force 3 ⁇ 400 ⁇ ⁇ or less As an evaluation standard, initial value of connection resistance R force 3 ⁇ 400 ⁇ ⁇ or less, resistance change rate A R A R
- sample No. 1 has an initial value of connection resistance because the total content of metal powder (Sn-58Bi powder and Cu powder) is less than 70 wt% and 75 wt%.
- R is 4
- the adhesion strength after PCT is 14N / mm 2 and is reduced to 20N / mm 2 or less. did. This is because the content of the metal powder in the conductive bonding material is small, so the Sn-58Bi powder does not sufficiently spread during heat curing, so that a sufficient conductive path is not generated and the melting point is 300 ° C or higher. It is considered that the high-melting point reaction product cannot be sufficiently obtained, so that the conductivity and adhesion strength after PCT are lowered and the moisture resistance is deteriorated.
- Sample No. 6 has a total content of metal powders (Sn-58Bi powder and Cu powder) exceeding 93 wt% and 88 wt%, so that the bond strength is 7N / mm even at the initial value S. 2 and lower PC
- Sample No. 25 has a total content of metal powder of 75 88 wt%, but the average particle size D1 of Sn-58Bi powder and the average particle size D2 of Cu powder Since the ratio D1 / D2 is 2.0, which is within the range of the present invention, and the volume ratio of Sn-58Bi powder to the total amount of metal powder is 50% by volume, the initial value R of the connection resistance is 2; 130 ⁇ ⁇ after PCT
- Resistance change rate A R force 3 ⁇ 4 ⁇ ; 16%, resistance change rate after reflow A R force 3 ⁇ 4 25%, sticking
- Sample No. 3 4 with a total metal powder content of 83 86 wt% has an initial connection resistance value R of 2 ;! 58 ⁇ ⁇ Resistance change after PCT Rate AR force 3 ⁇ 4 to 8%, resistance change rate after reflow AR force 3 ⁇ 4 25%, initial bond strength
- the sample No. 2 was embedded in the resin, polished, and the cross section of the interface between the land electrode and the external electrode was observed.
- the Sn-58Bi powder dispersed in the conductive bonding material was found to be High-melting point reactants are formed between Sn forming the external electrode, Ag-Pd forming the land electrode, and Cu powder, which ensures good connection reliability. It has been certified.
- the initial value S was measured, and each resistance change rate A R A R after PCT and after reflow treatment, and
- Table 2 shows the specifications and experimental results of the conductive bonding materials of sample numbers 11 to 16;
- Sample No. 11 has a total content of metal powder (Sn-58Bi powder and Sn-coated Cu powder) of less than 70 wt% and 75 wt%.
- Sample No. 12 15 has a metal powder content of 75 88% by weight, and is composed of an average particle diameter D1 of Sn-58Bi powder and an average particle diameter D2 of Sn-coated Cu powder. Since the diameter ratio D1 / D2 is 2.0, which is within the range of the present invention, and the volume ratio of Sn-58Bi powder to the total metal powder is a preferable range of 50% by volume, the initial value of connection resistance R force 3 to 102 ⁇ ⁇ P
- Resistance change rate A R force 3 ⁇ 4 ⁇ 4%, resistance change rate after reflow A R force 18%, adhesion strength
- connection resistance and the fixing strength were improved as a whole. This seems to be because the Cu powder was coated with Sn, which has high wettability to Sn-58Bi powder, which facilitated the formation of conductive paths and the generation of high melting point reactants.
- the initial value S is measured, and the resistance change rates A R, A R, and
- Table 3 shows the specifications and experimental results of the conductive bonding materials of sample numbers 2;!
- Sample No. 21 has a resistance change rate after PCT of AR force 3 ⁇ 4 10%. Over 200%. This is because the average particle diameter D1 of Sn-58Bi powder is too small compared to the spacing between Sn-coated Cu powders, so even if Sn-58Bi powder wets and spreads during heat-curing, Sn-coated Cu powders can be replaced with Sn-58Bi powder. As a result, it is impossible to form a conductive path with good conductivity, and as a result, the connection resistance rises when exposed to high temperature and high humidity for a long time. It is thought that the nature decreases.
- Sample No. 2 ;! 24 has a particle size ratio D1 / D2 of 0.5 6.0 and a total content of metal powder (Sn-58Bi powder and Sn-coated Cu powder) of 86. Since the preferred volume ratio of Sn-58Bi powder to the total amount of metal powder is 50% by volume, the initial value of connection resistance R force 3 ⁇ 46 71 ⁇ ⁇ Resistance change after PCT Rate ⁇
- sample number 22 2 3 having a particle size ratio D1 / D2 of 0.5 2.0 is the initial value of connection resistance R force 3 ⁇ 46 48 ⁇ Resistance change rate after PCT AR force ⁇ ; 18%
- Example 4 [0102] Sn-58Bi powder and Sn-coated Cu powder were prepared, and the volume ratio of Sn-58Bi powder to the total amount of metal powder (Sn-58Bi powder and Sn-coated Cu powder) in the same manner as in [Example 1] However, the conductive bonding materials of Sample Nos. 3;! To 36, which are different in the range of 20 to 80% by volume, were produced in the same manner as in [Example 1].
- the initial value S is measured, and the resistance change rates A R, A R, and
- Table 4 shows the specifications and experimental results of the conductive bonding materials of sample numbers 31 to 36.
- the volume ratio of the Sn-58Bi powder to the total amount of the metal powder is 20% by volume, which is as low as 25% by volume or less. This prevents the formation of a conductive path, and therefore the initial value R of the connection resistance is 110.
- the volume ratio of the Sn- 58Bi powder to the total amount of the metal powder is 80 vol 0 / o, because it exceeds 75 volume 0/0, does not react with Sn-coated Cu powder Sn — 58B i powder remains unreacted, so the initial value of connection resistance R force 3 ⁇ 400 ⁇ ⁇ , PCT
- the volume ratio of Sn-58Bi powder to the total amount of metal powder was preferably 25 to 75% by volume.
- sample number was used except that an In-coated Cu powder in which an average particle diameter D2 was coated with Cu powder having a thickness of 0.01 am coated on a Cu powder with a particle diameter of 5 m was used.
- a conductive bonding material of Sample No. 42 was produced by the same method and procedure as in 41.
- a conductive bonding material of Sample No. 43 was produced by the same method and procedure as Sample No. 42, except that the reducing substance was not added in the process of preparing the conductive bonding material. [0113] Next, the initial value R of the connection resistance and the initial sticking strength were the same as in [Example 1].
- Table 5 shows the specifications and experimental results of the conductive bonding materials of sample numbers 41 to 43.
- sample No. 43 has an initial connection resistance value R of 7300 m ⁇ .
- the conductivity decreased, the resistance change rate A Rl after PCT also increased to 790%, and the adhesion strength after PCT also decreased to 9 N / mm 2 .
- the conductive bonding material does not contain a reducing agent, so that the oxide remains on the surface of the In-coated Cu powder, so that Sn-58Bi powder is not heated during thermosetting of the thermosetting resin. This seems to be because the formation of a high-melting-point reactant that wets and spreads on the surface of the In coat Cu powder is not promoted.
- Sample Nos. 41 and 42 contain succinic acid as a reducing substance in the conductive bonding material, and the total content of the metal powder is 86% by weight, and the particle size ratio D1 / D2 is 2.0 and both are within the scope of the present invention, and the volume ratio of the Sn-58Bi powder to the total amount of the metal powder is a preferable range of 50% by volume. Therefore, the initial value of the connection resistance R force 3 ⁇ 4; 28
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Physics & Mathematics (AREA)
- Dispersion Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Inorganic Chemistry (AREA)
- Conductive Materials (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Electric Connection Of Electric Components To Printed Circuits (AREA)
Description
Claims
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008532041A JP5170685B2 (ja) | 2006-08-28 | 2007-08-24 | 導電性接合材料、及び電子装置 |
| EP07806061A EP2058822A4 (en) | 2006-08-28 | 2007-08-24 | CONDUCTIVE BINDER AND ELECTRONIC DEVICE |
| KR1020097003974A KR101056558B1 (ko) | 2006-08-28 | 2007-08-24 | 도전성 접합재료 및 전자장치 |
| US12/394,113 US8222751B2 (en) | 2006-08-28 | 2009-02-27 | Electroconductive bonding material and electronic apparatus |
| US12/959,752 US8105687B2 (en) | 2006-08-28 | 2010-12-03 | Electroconductive bonding material and electronic apparatus |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006-230726 | 2006-04-28 | ||
| JP2006230726 | 2006-08-28 |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US12/394,113 Continuation US8222751B2 (en) | 2006-08-28 | 2009-02-27 | Electroconductive bonding material and electronic apparatus |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2008026517A1 true WO2008026517A1 (en) | 2008-03-06 |
Family
ID=39135800
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/JP2007/066475 Ceased WO2008026517A1 (en) | 2006-08-28 | 2007-08-24 | Conductive bonding material and electronic device |
Country Status (6)
| Country | Link |
|---|---|
| US (2) | US8222751B2 (ja) |
| EP (1) | EP2058822A4 (ja) |
| JP (1) | JP5170685B2 (ja) |
| KR (1) | KR101056558B1 (ja) |
| CN (1) | CN101506906A (ja) |
| WO (1) | WO2008026517A1 (ja) |
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| CN110050036A (zh) * | 2016-12-09 | 2019-07-23 | 日立化成株式会社 | 组合物、粘接剂、烧结体、接合体和接合体的制造方法 |
| WO2018105126A1 (ja) * | 2016-12-09 | 2018-06-14 | 日立化成株式会社 | 組成物、接着剤、焼結体、接合体及び接合体の製造方法 |
| WO2018105125A1 (ja) * | 2016-12-09 | 2018-06-14 | 日立化成株式会社 | 組成物、接着剤、焼結体、接合体及び接合体の製造方法 |
| JPWO2018116692A1 (ja) * | 2016-12-19 | 2019-10-24 | タツタ電線株式会社 | パッケージ基板及びパッケージ基板の製造方法 |
| JP7041075B2 (ja) | 2016-12-19 | 2022-03-23 | タツタ電線株式会社 | パッケージ基板及びパッケージ基板の製造方法 |
| JP2021531358A (ja) * | 2018-05-16 | 2021-11-18 | ヘンケル・アクチェンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト・アウフ・アクチェンHenkel AG & Co. KGaA | ダイアタッチのための硬化性接着剤組成物 |
| JP7461890B2 (ja) | 2018-05-16 | 2024-04-04 | ヘンケル・アクチェンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト・アウフ・アクチェン | ダイアタッチのための硬化性接着剤組成物 |
| US12590228B2 (en) | 2018-05-16 | 2026-03-31 | Henkel Ag & Co. Kgaa | Curable adhesive composition for die attach |
| JP2021197540A (ja) * | 2020-06-16 | 2021-12-27 | インテル・コーポレーション | ブリッジを含むマイクロエレクトロニクス構造体 |
| JP7736396B2 (ja) | 2020-06-16 | 2025-09-09 | インテル・コーポレーション | マイクロエレクトロニクス構造体、マイクロエレクトロニクスアセンブリおよびエレクトロニクスデバイス |
Also Published As
| Publication number | Publication date |
|---|---|
| US8222751B2 (en) | 2012-07-17 |
| JP5170685B2 (ja) | 2013-03-27 |
| US20090155608A1 (en) | 2009-06-18 |
| KR20090037961A (ko) | 2009-04-16 |
| KR101056558B1 (ko) | 2011-08-11 |
| JPWO2008026517A1 (ja) | 2010-01-21 |
| US8105687B2 (en) | 2012-01-31 |
| CN101506906A (zh) | 2009-08-12 |
| EP2058822A1 (en) | 2009-05-13 |
| US20110067912A1 (en) | 2011-03-24 |
| EP2058822A4 (en) | 2011-01-05 |
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