TWI555818B - Thermal follower - Google Patents
Thermal follower Download PDFInfo
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- TWI555818B TWI555818B TW100149710A TW100149710A TWI555818B TW I555818 B TWI555818 B TW I555818B TW 100149710 A TW100149710 A TW 100149710A TW 100149710 A TW100149710 A TW 100149710A TW I555818 B TWI555818 B TW I555818B
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- conductive adhesive
- heat
- solder powder
- thermally conductive
- thermal
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- 239000000853 adhesive Substances 0.000 claims description 125
- 230000001070 adhesive effect Effects 0.000 claims description 124
- 229910052751 metal Inorganic materials 0.000 claims description 65
- 239000002184 metal Substances 0.000 claims description 65
- 229910000679 solder Inorganic materials 0.000 claims description 63
- 239000000843 powder Substances 0.000 claims description 58
- 238000002844 melting Methods 0.000 claims description 44
- 230000008018 melting Effects 0.000 claims description 43
- 239000000945 filler Substances 0.000 claims description 37
- 239000000758 substrate Substances 0.000 claims description 32
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 30
- 229920001187 thermosetting polymer Polymers 0.000 claims description 29
- 238000001723 curing Methods 0.000 claims description 27
- 239000004848 polyfunctional curative Substances 0.000 claims description 22
- 239000003822 epoxy resin Substances 0.000 claims description 21
- 229920000647 polyepoxide Polymers 0.000 claims description 21
- 230000017525 heat dissipation Effects 0.000 claims description 20
- 239000003795 chemical substances by application Substances 0.000 claims description 17
- 238000013007 heat curing Methods 0.000 claims description 10
- 238000001029 thermal curing Methods 0.000 claims description 10
- 229910045601 alloy Inorganic materials 0.000 claims description 9
- 239000000956 alloy Substances 0.000 claims description 9
- 230000004907 flux Effects 0.000 claims description 8
- 238000011049 filling Methods 0.000 claims description 7
- 230000000694 effects Effects 0.000 claims description 6
- 229910020830 Sn-Bi Inorganic materials 0.000 claims description 5
- 229910018728 Sn—Bi Inorganic materials 0.000 claims description 5
- 229910018956 Sn—In Inorganic materials 0.000 claims description 4
- 150000002762 monocarboxylic acid derivatives Chemical group 0.000 claims description 4
- 239000000155 melt Substances 0.000 claims description 3
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 150000003627 tricarboxylic acid derivatives Chemical class 0.000 claims 1
- 238000011156 evaluation Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 238000000113 differential scanning calorimetry Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000977 initiatory effect Effects 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 150000008065 acid anhydrides Chemical class 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 230000005496 eutectics Effects 0.000 description 3
- 230000001747 exhibiting effect Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- -1 propylene sulfonyl ethyl Chemical group 0.000 description 3
- FWHUTKPMCKSUCV-UHFFFAOYSA-N 1,3-dioxo-3a,4,5,6,7,7a-hexahydro-2-benzofuran-5-carboxylic acid Chemical compound C1C(C(=O)O)CCC2C(=O)OC(=O)C12 FWHUTKPMCKSUCV-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- 229910020994 Sn-Zn Inorganic materials 0.000 description 2
- 229910009069 Sn—Zn Inorganic materials 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 2
- 238000000635 electron micrograph Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 150000003628 tricarboxylic acids Chemical class 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- WTNDADANUZETTI-UHFFFAOYSA-N cyclohexane-1,2,4-tricarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)C(C(O)=O)C1 WTNDADANUZETTI-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- BXKDSDJJOVIHMX-UHFFFAOYSA-N edrophonium chloride Chemical compound [Cl-].CC[N+](C)(C)C1=CC=CC(O)=C1 BXKDSDJJOVIHMX-UHFFFAOYSA-N 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
-
- 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
- H05K7/00—Constructional details common to different types of electric apparatus
- H05K7/20—Modifications to facilitate cooling, ventilating, or heating
- H05K7/2039—Modifications to facilitate cooling, ventilating, or heating characterised by the heat transfer by conduction from the heat generating element to a dissipating body
-
- 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
- C09J201/00—Adhesives based on unspecified macromolecular compounds
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- 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
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- 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
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/50—Assembly of semiconductor devices using processes or apparatus not provided for in a single one of the subgroups H01L21/06 - H01L21/326, e.g. sealing of a cap to a base of a container
- H01L21/52—Mounting semiconductor bodies in containers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/34—Arrangements for cooling, heating, ventilating or temperature compensation ; Temperature sensing arrangements
- H01L23/36—Selection of materials, or shaping, to facilitate cooling or heating, e.g. heatsinks
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/34—Arrangements for cooling, heating, ventilating or temperature compensation ; Temperature sensing arrangements
- H01L23/36—Selection of materials, or shaping, to facilitate cooling or heating, e.g. heatsinks
- H01L23/373—Cooling facilitated by selection of materials for the device or materials for thermal expansion adaptation, e.g. carbon
- H01L23/3737—Organic materials with or without a thermoconductive filler
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
- H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L24/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
- H01L24/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
- H01L24/29—Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
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- 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
- C08K2003/0806—Silver
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- C—CHEMISTRY; METALLURGY
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- 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
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
- H01L2224/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
- H01L2224/29—Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
- H01L2224/29001—Core members of the layer connector
- H01L2224/29099—Material
- H01L2224/29198—Material with a principal constituent of the material being a combination of two or more materials in the form of a matrix with a filler, i.e. being a hybrid material, e.g. segmented structures, foams
- H01L2224/29298—Fillers
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/42—Wire connectors; Manufacturing methods related thereto
- H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
- H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
- H01L2224/4805—Shape
- H01L2224/4809—Loop shape
- H01L2224/48091—Arched
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/73—Means for bonding being of different types provided for in two or more of groups H01L2224/10, H01L2224/18, H01L2224/26, H01L2224/34, H01L2224/42, H01L2224/50, H01L2224/63, H01L2224/71
- H01L2224/732—Location after the connecting process
- H01L2224/73251—Location after the connecting process on different surfaces
- H01L2224/73265—Layer and wire connectors
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/013—Alloys
- H01L2924/0132—Binary Alloys
- H01L2924/01322—Eutectic Alloys, i.e. obtained by a liquid transforming into two solid phases
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- H—ELECTRICITY
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/06—Polymers
- H01L2924/078—Adhesive characteristics other than chemical
- H01L2924/0781—Adhesive characteristics other than chemical being an ohmic electrical conductor
- H01L2924/07811—Extrinsic, i.e. with electrical conductive fillers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/10—Details of semiconductor or other solid state devices to be connected
- H01L2924/11—Device type
- H01L2924/12—Passive devices, e.g. 2 terminal devices
- H01L2924/1204—Optical Diode
- H01L2924/12041—LED
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Thermal Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Die Bonding (AREA)
- Cooling Or The Like Of Semiconductors Or Solid State Devices (AREA)
- Conductive Materials (AREA)
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Description
本發明係關於一種於含有硬化成分及該硬化成分用之硬化劑的熱固性接著劑中,分散有金屬填料而成之導熱性接著劑。
為了將構裝於散熱基板之LED(發光二極體)晶片或IC(積體電路)晶片發出之熱經由散熱基板並散熱至散熱片(heat sink),而將散熱基板與散熱片藉由導熱性接著劑進行接著。作為此種導熱性接著劑,提出有使高熔點金屬粉末及低熔點金屬粉末作為金屬填料分散於熱固性接著劑而成(專利文獻1),該導熱性接著劑含有:作為具有助熔劑活性之硬化成分的二羧酸單(甲基)丙烯醯烷基乙酯、使該助熔劑活性於高溫去活化的環氧丙基醚系化合物、作為可成為硬化成分之稀釋劑的(甲基)丙烯酸系單體及自由基(radical)聚合起始劑。利用該導熱性接著劑之導熱係由如下燒結構造而實現:於熱固性接著劑中接著劑固化之前,將液化之低熔點金屬與高熔點金屬燒結所得的燒結構造。
專利文獻1:日本特開2006-523760號公報
然而,於專利文獻1揭示之導熱性接著劑的情形時,因以反應速度快之自由基聚合進行固化,故而擔心於低熔點金屬液化以使高熔點金屬粉間互相充分地連結之前導熱性接著劑便固化。因此,為了確保所需求之導熱性,以下
述式(1)定義之金屬填料填充率超過90%之方式摻合(實施例)。該方法由於相對降低熱固性接著劑之含量,而產生所謂使其接著力降低之其他問題。
金屬填料填充率(%)={金屬填料/(金屬填料+硬化成分+硬化劑)}×100(1)
本發明之目的係欲解決以上先前技術之課題,其目的在於:於具有含有硬化成分及該硬化成分用之硬化劑的熱固性接著劑、及分散於該熱固性接著劑中之金屬填料的導熱性接著劑中,能夠在導熱性接著劑固化前,使低熔點金屬液化並使高熔點金屬粉間互相充分地連結,且使導熱性接著劑本身之接著力維持在良好水平。
本發明人等發現:於使含有熱固性接著劑及金屬填料的導熱性接著劑熱固化之情形時,只要可於該熱固化物中形成金屬填料連續之網狀結構(network)(金屬之連續相),則可以較先前之導熱性接著劑相對少量的金屬填料來實現良好之導熱性,且可較先前之導熱性接著劑的熱固性接著劑含有比例變高,故而必然在可抑制導熱性接著劑之接著力降低的假設下,除銀粉以外,併用具有低於導熱性接著劑之熱固化處理溫度的熔融溫度,在導熱性接著劑之熱固化處理條件下與銀粉進行反應,而生成表現出高於該焊料粉熔融溫度之熔點之高熔點焊料合金的所謂低熔點焊錫粉,作為金屬填料;且使用具有助熔劑活性者,作為硬化劑;藉此可經由銀粉形成熔融焊料連續之網狀結構(金屬
之連續相),從而完成本發明。
即,本發明提供一種導熱性接著劑,其於含有硬化成分及該硬化成分用之硬化劑的熱固性接著劑中分散有金屬填料而成,其特徵在於:金屬填料具有銀粉及焊料粉;該焊料粉表現出低於導熱性接著劑之熱固化處理溫度的熔融溫度,並且於該導熱性接著劑之熱固化處理條件下與銀粉進行反應,而生成表現出高於該焊料粉熔融溫度之熔點的高熔點焊料合金;該硬化劑係對金屬填料具有助熔劑活性之硬化劑。
又,本發明提供一種功率LED模組,其中LED晶片藉由本發明之導熱性接著劑而固晶(die bond)構裝於散熱基板之表面,LED晶片之表面電極與散熱基板之表面電極藉由線結合(wire bonding)進行連接,且該散熱基板藉由本發明之導熱性接著劑而接著於散熱片(heat sink);一種功率LED模組,其中LED晶片係覆晶構裝於散熱基板之表面,該散熱基板藉由本發明之導熱性接著劑而接著於散熱片;又,一種功率IC模組,其中IC晶片藉由本發明之導熱性接著劑而固晶構裝於散熱基板之表面,IC晶片之表面電極與散熱基板之表面電極藉由線結合進行連接,且該散熱基板藉由本發明之導熱性接著劑而接著於散熱片。
於本發明之導熱性接著劑中,除銀粉以外,併用焊料粉作為金屬填料,焊料粉表現出低於導熱性接著劑之熱固化處理溫度的熔融溫度,並且於該導熱性接著劑之熱固化
處理條件下與銀粉進行反應,而生成顯示出高於該焊料粉熔融溫度之熔點的高熔點焊料合金。因此,於使導熱性接著劑熱固化時,在達到其熱固化處理溫度之前熔融焊料粉。又,由於使用具有助熔劑活性者作為硬化劑,故而可提高熔融之焊料對銀粉的潤濕性。因此,可於導熱性接著劑之熱固化物中,利用相對少量之熔融金屬填料經由銀粉而形成連續之網狀結構(金屬之連續相),可高效率地實現導熱。因此,可使熱固性接著劑之含量相對增大,可提高導熱性接著劑之硬化物的接著力。
又,熔融之焊料粉在導熱性接著劑之熱固化處理條件下進而與銀粉進行反應,生成表現出高於該焊料粉熔融溫度之熔點的高熔點焊料合金。因此,可提高導熱性接著劑之硬化物的耐熱性。
進而,由於硬化劑本身與硬化成分一併作為一聚合單元而併入於硬化物中,故而亦不會產生硬化劑之白化(blooming)。因此,可防止起因於此種溢出之導熱性接著劑之接著力降低。
本發明之導熱性接著劑係具有含有硬化成分及該硬化成分用之硬化劑的熱固性接著劑、及分散於該熱固性接著劑中的金屬填料者。此處,金屬填料含有銀粉及焊料粉。首先,對熱固性接著劑進行說明,繼而對金屬填料進行說明。
<熱固性接著劑>
可使用藉由熱固化處理而與硬化劑具有接著作用之環氧樹脂、酚樹脂、胺酯樹脂等,作為構成熱固性接著劑之硬化成分,其中為了助熔劑成分之去活化,較佳為使用環氧樹脂。作為此種環氧樹脂,可舉例雙酚A型環氧樹脂、雙酚F型環氧樹脂、酚醛清漆型環氧樹脂等環氧丙基醚型環氧樹脂。另外,可使用脂環族環氧樹脂或含雜環之環氧樹脂等通常已知者。再者,較佳為於反應速度相對較快的脂環族環氧樹脂之情形時,隨著其使用而加快導熱性接著劑之硬化速度,藉此,利用熔融焊料粉而更迅速地進行網狀結構(金屬之連續相)形成。於該情形時,只要使用更低熔點之焊料粉即可。
又,使用對應於硬化成分之硬化劑且具有助熔劑活性者,作為硬化劑。於硬化成分為環氧樹脂之情形時,不會於熱固化時產生氣體,可在與環氧樹脂進行混合時實現較長適用期(pot life),又,就可實現所獲得硬化物之電特性、化學特性及機械特性間的良好平衡性方面而言,較佳為使用酸酐作為硬化劑。
又,使硬化劑表現出助熔劑活性之方法,可列舉利用公知之方法於硬化劑導入羧基、磺醯基、磷酸基等質子酸基之方法。其中,就與環氧樹脂之反應性方面而言,較佳應用羧基。
因此,作為硬化成分為環氧樹脂之情形時之較佳硬化劑,可列舉:存在自由羧基之三羧酸之單酸酐,較佳為環己烷-1,2,4-三羧酸-1,2-酸酐。
熱固性接著劑中硬化成分與硬化劑之含有比例依硬化成分或硬化劑之種類而有不同,於硬化成分為環氧樹脂,硬化劑為三羧酸之單酸酐之情形時,環氧樹脂之含量相對過多或過少均會使硬化不充分,故而以莫耳當量基準之當量比([環氧樹脂]/[硬化劑])計較佳為1:0.5~1:1.5,更佳為1:0.8~1:1.2。
於熱固性接著劑,除上述硬化成分及硬化劑以外,亦可於不損害發明效果之範圍內添加公知之摻合於導熱性接著劑的各種添加劑,例如:顏料、紫外線吸收劑、硬化促進劑、矽烷偶合劑。
用以構成導熱性接著劑之熱固性接著劑可藉由利用通常之方法將硬化成分或硬化劑、及其他添加劑均勻地混合而製備。
<金屬填料>
分散於上述熱固性接著劑用以製備導熱性接著劑之金屬填料含有銀粉與焊料粉。
由於銀粉之導熱率高且熔點高,且不會因導熱性接著劑普遍的熱固化處理時之加熱而熔融,故而為了僅使用銀粉作為金屬填料而實現效率佳之導熱,必需使未熔融之銀粉彼此接觸。故而,於導熱性接著劑摻合大量銀粉,但是若摻合大量之銀粉,則有熱固性接著劑含量相對減少且接著力降低之虞。因此,本發明中,作為摻合於導熱性接著劑之金屬填料的總量之一部分,使用表現出熱固化溫度附近之熔融溫度的焊料粉,利用熔融之焊料粉使銀粉間網狀
結構化(金屬之連續相化)。
作為以此種目的使用之焊料粉,具體而言,使用表現出低於導熱性接著劑之熱固化處理溫度的熔融溫度,並且在該導熱性接著劑之熱固化處理條件下與銀粉進行反應,而生成表現出高於該焊料粉熔融溫度之熔點的高熔點焊料合金者。藉此可提高導熱性接著劑之硬化物的耐熱性。
作為此種焊料粉,可較佳列舉:Sn-Bi系焊料粉、Sn-In系焊料粉、Sn-Zn系焊料粉,其中,就低溫溶融性之觀點而言,較佳可列舉:Sn-Bi系焊料粉、Sn-In系焊料粉。作為Sn-Bi系焊料粉之具體例,可列舉Sn-58Bi共晶系焊料粉(熔點139℃);作為Sn-In系焊料粉,可列舉Sn-52In共晶系焊料粉(熔點117℃);作為Sn-Zn系焊料粉之具體例,可列舉Sn-9Zn共晶系焊料粉(熔點199℃)。
作為銀粉及焊料粉之粒子形狀,可列舉:球狀、扁平狀、粒狀、針狀等形狀。
銀粉與焊料粉之質量比,由於若前者過多則有網狀結構(金屬之連續相)變少之傾向,若前者過少則有高熔點焊料之生成量變少之傾向,故而較佳為以質量比計為1:2~2:1,更佳為1:1.5~1.5:1。
<導熱性接著劑>
本發明之導熱性接著劑係藉由利用普遍之方法將以上說明之金屬填料與熱固性接著劑均勻地進行混合所製備者,亦可視需要添加有機溶劑。此處,關於金屬填料之導
熱性接著劑中的含量(即,於以下之式(1)定義之質量基準的金屬填料填充率),若過低則有難以形成網狀結構(金屬之連續相)之傾向,若過高則有導熱性接著劑之接著力降低之傾向,故而較佳為75~95%,更佳為80~90%。
金屬填料填充率(%)={金屬填料/(金屬填料+硬化成分+硬化劑)}×100(1)
本發明之導熱性接著劑可較佳應用於將構裝有LED晶片或IC晶片之散熱基板接著於散熱片,以構成功率LED模組或功率IC模組時。此處,作為功率LED模組,有線結合構裝型者(圖3)及覆晶構裝型者(圖4),作為功率IC模組,有線結合構裝型者(圖5)。
圖3之線結合構裝型的功率LED模組300具有如下構造:LED晶片30藉由本發明之導熱性接著劑31而固晶構裝於散熱基板32,LED晶片30之表面電極(未圖示)與散熱基板32之表面電極(未圖示)藉由線結合進行連接(具體而言藉由接線33(bonding wire)進行連接),該散熱基板32進而藉由本發明之導熱性接著劑34而接著於散熱片35。於該功率LED模組300中,LED晶片30發出之熱依序傳導至導熱性接著劑31之硬化物、散熱基板32、導熱性接著劑34之硬化物、散熱片35,而會防止因LED晶片30之熱引起之性能降低。
圖4之覆晶構裝型的功率LED模組400具有如下構造:LED晶片40藉由公知的熱固性異向性導電接著劑等接
著劑41而覆晶構裝於散熱基板42,該散熱基板42進而藉由本發明之導熱性接著劑43而接著於散熱片44。於該功率LED模組400中,LED晶片40發出之熱依序傳導至接著劑41、散熱基板42、導熱性接著劑43之硬化物、散熱片44,而會防止因LED晶片40之熱引起之性能降低。
圖5之線結合構裝型的功率IC模組500具有如下結構:IC晶片50藉由本發明之導熱性接著劑51而固晶構裝於散熱基板52之表面,IC晶片50之表面電極(未圖示)與散熱基板52之表面電極(未圖示)藉由線結合進行連接(具體而言係藉由接線53進行連接),該散熱基板52藉由本發明之導熱性接著劑54而接著於散熱片55。於該功率IC模組500中,IC晶片50發出之熱依序傳導至導熱性接著劑51、散熱基板52、導熱性接著劑54、散熱片55,而會防止因IC晶片50之熱引起之性能降低。
於圖3~圖5之功率LED模組(300、400)或功率IC模組(500)中,為了提高散熱效率,可於散熱基板(32、42、52)與散熱片(35、44、55)之間,使用本發明之導熱性接著劑分別夾持熱擴散板。
再者,於圖3~圖5之模組中,使用本發明之導熱性接著劑以外之構成可與公知的功率LED模組或功率IC模組之構成相同。
[實施例]
實施例1
將100質量份之雙酚F型環氧樹脂(jER806,三菱化
學(股))作為硬化成分、70質量份之環己烷-1,2,4-三羧酸-1,2-酸酐(H-TMAn/H-TMAn-S,三菱瓦斯化學(股))作為硬化劑、340質量份之平均粒徑20μm之Sn-58Bi焊料粉(Sn-Bi,三井金屬礦業(股))及340質量份之銀粉(AgC-224,福田金屬箔粉工業(股))作為金屬填料,利用攪拌裝置(練太郎脫泡攪拌自動公轉混合機,Thinky(股))均勻地進行混合,從而獲得實施例1之膏狀(paste)導熱性接著劑。金屬填料填充率為80%。再者,將作為硬化成分之環氧樹脂與作為硬化劑之環己烷-1,2,4-三羧酸-1,2-酸酐的莫耳當量基準當量比([環氧樹脂]/[硬化劑])示於表1中。
對獲得之熱固化處理前之導熱性接著劑,及進行熱固化處理(於150℃下加熱60分鐘)後之導熱性接著劑之硬化物,進行差式掃描熱量測定(測定裝置:DSC Q100,TA Instruments公司,升溫速度為10℃/min,掃描溫度區域為10~300℃)。將獲得之結果(DSC差式掃描熱量測定圖)示於圖1中。又,對導熱性接著劑之硬化物進行剖面研磨,並利用切割面之掃描型電子顯微鏡(S-3000N,日立製作所(股))進行拍攝。將所獲得之電子顯微鏡照片示於圖2。
於圖1之硬化前的DSC曲線中,於約140℃觀察到隨著Sn-58Bi焊料熔融之吸熱,於150-160℃附近觀察到熱固性接著劑之放熱,於260℃附近觀察到隨著Sn-3.5Ag熔融之吸熱。又,於硬化後之DSC曲線中,140℃附近之Sn-Bi焊料熔融時之吸熱與150-160℃附近之導熱性接著劑
硬化時之放熱均無法觀察到,但於260℃附近,觀察到隨著Sn-3.5Ag熔融之明顯之吸熱。
於圖2之電子顯微鏡照片,觀察到黑色、灰色、高亮度之三種不同亮度區域。高亮度為Bi、灰色區域為高熔點焊料合金及銀粉。黑色區域為熱固性接著劑之硬化物。如此,觀察到於高亮度與灰色之區域形成網狀結構(金屬之連續相)。再者,可認為藉由熱固化處理而新生成之高熔點焊料合金係包含於照片上灰色區域。
又,針對獲得之導熱性接著劑,藉由以下之方式對「低溫硬化性」、「網狀結構(金屬之連續相)形成性」、「導熱率」、及「接著強度」進行試驗、評價,將獲得之結果示於表1。
<低溫硬化性>
將焊料粉之熔融溫度及導熱性接著劑之硬化起始溫度均為200℃以下,且熔融溫度低於硬化起始溫度之情形評價為「◎」,將焊料粉之熔融溫度及導熱性接著劑之硬化起始溫度均為200℃以下,但熔融溫度不低於硬化起始溫度之情形評價為「○」,其以外之情形評價為「×」。
<網狀結構形成性>
切割導熱性接著劑之硬化物,並對其切割面進行研磨,利用掃描型電子顯微鏡(S-3000N,日立製作所(股))拍攝該研磨面,並觀察是否有利用焊料粉形成之網狀結構(金屬之連續相)。
<導熱率>
使用導熱率測定裝置(LFA447NanoFlash,Netzsch公司製造)對導熱性接著劑之硬化物的導熱率進行測定。將獲得之測定結果的導熱率為8.0W/mk以上之情形評價為「◎」,將5.0W/mk以上、未達8.0W/mk之情形評價為「○」,將未達5.0W/mk之情形評價為「×」。
<接著強度>
於2片100mm×15mm×0.5mm之鋁板(A5052P)間以直徑成為10mm之方式而夾入導熱性接著劑(2片鋁板之接觸面積:15mm×15mm),於150℃實施60分鐘烘箱固化(oven cure),製作測定樣品,利用拉伸試驗機(Tensilon,Orientec公司),測定剪力(shear)強度(25℃下拉伸速度為5mm/min)。將獲得之測定結果接著強度為130kN/cm2以上之情形評價為「◎」,將100kN/cm2以上未達130kN/cm2之情形評價為「○」,將未達100kN/cm2之情形評價為「×」。
實施例2~7、比較例1~4
使用表1中所示之成分,並反覆進行與實施例1相同之操作,藉此獲得實施例2~7、比較例1~4之膏狀導熱性接著劑。針對所獲得之導熱性接著劑,以與實施例1之情形相同,對「低溫硬化性」、「網狀結構(金屬之連續相)形成性」、「導熱率」、及「接著強度」進行試驗、評價,將獲得之結果示於表1中。
由表1可知,環氧樹脂與硬化劑之莫耳當量比為1:0.8~1:1.2之範圍的實施例1~7導熱性接著劑,於低溫硬化性、網狀結構(金屬之連續相)形成性、導熱率及接著強度中任一項評價項目均表現出良好之結果。
另一方面,於比較例1之情形時,由於使用無助熔劑活性之酸酐作為硬化劑,且焊料粉之熔融物未將銀粉充分潤濕,故而未形成網狀結構(金屬之連續相),導熱率之評價低。於比較例2之情形時,由於使用無助熔劑活性之酸酐作為硬化劑,且焊料粉之熔融物未將銀粉充分潤濕,故而未形成網狀結構(金屬之連續相),雖然由於使金屬填料
填充率增大故而導熱率之評價較佳,但是由於熱固性接著劑之量相對減少故而接著強度降低。於比較例3之情形時,由於未使用銀粉,其為於熔融之焊料粉形成網狀結構時之核,故而未形成網狀結構(金屬之連續相),且導熱率之評價較低。於比較例4之情形時,由於未使用形成網狀結構(金屬之連續相)之焊料粉,故而未形成網狀結構(金屬之連續相),且導熱率評價較低。
[產業上之可利用性]
本發明之導熱性接著劑可於導熱性接著劑之熱固化物中以相對少量之熔融金屬填料經由銀粉形成連續之網狀結構(金屬之連續相),可實現高效率之導熱。因此,可使熱固性接著劑之含量相對增大,可提高導熱性接著劑之硬化物的接著力。又,熔融之焊料粉在導熱性接著劑之熱固化處理條件下進而與銀粉進行反應,而生成表現出高於該焊料粉熔融溫度之熔點的高熔點焊料合金。因此,可提高導熱性接著劑之硬化物的耐熱性。因此,本發明之導熱性接著劑可用於功率LED模組或功率IC模組中散熱片之接著。
30、40‧‧‧LED晶片
31、34、43、51、54‧‧‧導熱性接著劑
32、42、52‧‧‧散熱基板
33、53‧‧‧接線
35、44、55‧‧‧散熱片
41‧‧‧接著劑
50‧‧‧IC晶片
300‧‧‧線結合構裝型之功率LED模組
400‧‧‧覆晶構裝型之功率LED模組
500‧‧‧線結合構裝型之功率IC模組
圖1係實施例1之導熱性接著劑之硬化前、硬化後的DSC(差式掃描熱量測定)圖。
圖2係實施例1之導熱性接著劑之硬化後的剖面照片。
圖3係本發明之線結合構裝型之功率LED模組的概略剖面圖。
圖4係本發明之覆晶構裝型之功率LED模組的概略剖
面圖。
圖5係本發明之線結合構裝型之功率IC模組的概略剖面圖。
Claims (9)
- 一種導熱性接著劑,係具有:含有硬化成分及該硬化成分用之硬化劑的熱固性接著劑、及分散於該熱固性接著劑中的金屬填料,其特徵在於:金屬填料具有銀粉及焊料粉;該焊料粉表現出低於導熱性接著劑之熱固化處理溫度的熔融溫度,並且於該熱固性接著劑之熱固化處理條件下與銀粉進行反應,而生成表現出高於該焊料粉熔融溫度之熔點的高熔點焊料合金;該硬化劑係對金屬填料具有助熔劑活性的硬化劑;該硬化成分為環氧丙基醚型環氧樹脂,硬化劑為三羧酸之單酸酐。
- 如申請專利範圍第1項之導熱性接著劑,其中,該焊料粉係Sn-Bi系焊料粉或Sn-In系焊料粉。
- 如申請專利範圍第1或2項之導熱性接著劑,其中,銀粉與焊料粉之質量比為1:2~2:1。
- 如申請專利範圍第1或2項之導熱性接著劑,其中,質量基準之金屬填料填充率為75~95%。
- 如申請專利範圍第1項之導熱性接著劑,其中,莫耳當量基準的硬化成分與硬化劑之當量比([環氧樹脂]:[硬化劑])為1:0.5~1:1.5。
- 如申請專利範圍第1項之導熱性接著劑,其中,於熱固化時,該焊料粉熔融並於銀粉間形成網狀結構。
- 一種功率LED模組,其中,LED晶片藉由申請專利 範圍第1至6項中任一項之導熱性接著劑而固晶構裝於散熱基板之表面,LED晶片之表面電極與散熱基板之表面電極藉由線結合進行連接,該散熱基板藉由申請專利範圍第1至6項中任一項之導熱性接著劑而接著於散熱片。
- 一種功率LED模組,其中,LED晶片覆晶構裝於散熱基板之表面,該散熱基板藉由申請專利範圍第1至6項中任一項之導熱性接著劑而接著於散熱片。
- 一種功率IC模組,其中,IC晶片藉由申請專利範圍第1至6項中任一項之導熱性接著劑而固晶構裝於散熱基板之表面,IC晶片之表面電極與散熱基板之表面電極藉由線結合進行連接,該散熱基板藉由申請專利範圍第1至6項中任一項之導熱性接著劑而接著於散熱片。
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KR102297961B1 (ko) * | 2019-11-11 | 2021-09-02 | 중앙대학교 산학협력단 | 저융점 및 고융점 필러를 포함하는 열 및 전기 전도성 경로를 형성할 수 있는 접착제 및 이를 이용한 솔더링 방법 |
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