JP5626179B2 - Film adhesive and semiconductor device using the same - Google Patents
Film adhesive and semiconductor device using the same Download PDFInfo
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- JP5626179B2 JP5626179B2 JP2011233035A JP2011233035A JP5626179B2 JP 5626179 B2 JP5626179 B2 JP 5626179B2 JP 2011233035 A JP2011233035 A JP 2011233035A JP 2011233035 A JP2011233035 A JP 2011233035A JP 5626179 B2 JP5626179 B2 JP 5626179B2
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- 239000004065 semiconductor Substances 0.000 title claims description 42
- 239000000853 adhesive Substances 0.000 title description 65
- 230000001070 adhesive effect Effects 0.000 title description 65
- 229920000647 polyepoxide Polymers 0.000 claims description 55
- 239000003822 epoxy resin Substances 0.000 claims description 52
- 239000011256 inorganic filler Substances 0.000 claims description 26
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 26
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 22
- 239000007787 solid Substances 0.000 claims description 22
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 15
- 229920000178 Acrylic resin Polymers 0.000 claims description 12
- 239000004925 Acrylic resin Substances 0.000 claims description 12
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 claims description 11
- 239000000377 silicon dioxide Substances 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 10
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- 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 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 125000002883 imidazolyl group Chemical group 0.000 claims description 3
- 229930185605 Bisphenol Natural products 0.000 claims 1
- 229920005989 resin Polymers 0.000 description 23
- 239000011347 resin Substances 0.000 description 23
- 230000000052 comparative effect Effects 0.000 description 15
- 238000002844 melting Methods 0.000 description 10
- 230000008018 melting Effects 0.000 description 10
- 230000007423 decrease Effects 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000013034 phenoxy resin Substances 0.000 description 5
- 229920006287 phenoxy resin Polymers 0.000 description 5
- 238000005259 measurement Methods 0.000 description 4
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 4
- 239000011354 acetal resin Substances 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 150000002460 imidazoles Chemical class 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 229920001721 polyimide Polymers 0.000 description 3
- 239000009719 polyimide resin Substances 0.000 description 3
- 229920006324 polyoxymethylene Polymers 0.000 description 3
- 239000003566 sealing material Substances 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- 239000002966 varnish Substances 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- QHIWVLPBUQWDMQ-UHFFFAOYSA-N butyl prop-2-enoate;methyl 2-methylprop-2-enoate;prop-2-enoic acid Chemical compound OC(=O)C=C.COC(=O)C(C)=C.CCCCOC(=O)C=C QHIWVLPBUQWDMQ-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 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 2
- 229920003986 novolac Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 1
- 239000004643 cyanate ester Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- -1 polyethylene terephthalate Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 238000001721 transfer moulding Methods 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/42—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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/42—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
- H01L2224/481—Disposition
- H01L2224/48151—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
- H01L2224/48221—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
- H01L2224/48225—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation
- H01L2224/48227—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation connecting the wire to a bond pad of the item
-
- 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
- H01L2224/73201—Location after the connecting process on the same surface
- H01L2224/73203—Bump and layer connectors
- H01L2224/73204—Bump and layer connectors the bump connector being embedded into the layer connector
-
- 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
-
- 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
- H01L2224/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
- H01L2224/83—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a layer connector
- H01L2224/8319—Arrangement of the layer connectors prior to mounting
- H01L2224/83192—Arrangement of the layer connectors prior to mounting wherein the layer connectors are disposed only on another item or body to be connected to the semiconductor or solid-state body
-
- 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
- H01L2224/91—Methods for connecting semiconductor or solid state bodies including different methods provided for in two or more of groups H01L2224/80 - H01L2224/90
- H01L2224/92—Specific sequence of method steps
- H01L2224/922—Connecting different surfaces of the semiconductor or solid-state body with connectors of different types
- H01L2224/9222—Sequential connecting processes
- H01L2224/92242—Sequential connecting processes the first connecting process involving a layer connector
- H01L2224/92247—Sequential connecting processes the first connecting process involving a layer connector the second connecting process involving a wire connector
Landscapes
- Adhesives Or Adhesive Processes (AREA)
- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
- Die Bonding (AREA)
- Adhesive Tapes (AREA)
Description
本発明は、半導体チップと回路基板との接続において、加熱圧接によって相対峙する電極を電気的に接続するフィルム状接着剤及びこれを用いた半導体装置に関する。 The present invention relates to a film adhesive for electrically connecting electrodes opposed to each other by heating and pressing in a connection between a semiconductor chip and a circuit board, and a semiconductor device using the same.
半導体チップを回路基板に固定し電気的に接続するために、熱硬化性の接着剤が用いられる（例えば、特許文献１参照）。この接着剤は、フィルム状あるいはペースト状の接着剤であり、あらかじめ半導体チップ側あるいは回路基板側に均一に配置することが容易で接続時間を短縮できる点からフィルム状接着剤の方が生産効率に優れる。 A thermosetting adhesive is used to fix and electrically connect the semiconductor chip to the circuit board (see, for example, Patent Document 1). This adhesive is a film-like or paste-like adhesive, and it is easier to arrange it on the semiconductor chip side or the circuit board side in advance and the connection time can be shortened. Excellent.
フリップチップ実装のように半導体チップの電極と回路基板の電極が相対峙する実装方法においてフィルム状の接着剤を使用する場合は、あらかじめ半導体チップあるいは回路基板側に接着剤を予め配置するために接着剤により電極表面が覆われてしまう。そのため、電極の表面から接着剤を排除し電極同士を電気的に接続するためには、接着剤を加熱して電極同士を強く押し合わせる必要がある。この接続は高荷重（およそ、１ＭＰａ／ｃｈｉｐ）で行われている。 When a film adhesive is used in a mounting method in which the electrode of the semiconductor chip and the electrode of the circuit board are opposed to each other as in flip chip mounting, the adhesive is used to place the adhesive in advance on the semiconductor chip or circuit board side. The electrode surface is covered with the agent. Therefore, in order to remove the adhesive from the surface of the electrode and to electrically connect the electrodes, it is necessary to heat the adhesive and strongly press the electrodes together. This connection is performed with a high load (approximately 1 MPa / chip).
近年、半導体チップのピン数は増加し、チップ厚みは減少する傾向にあり、半導体チップ一個当りに必要な接続荷重は増加している。一方、チップ厚みの薄肉化に伴い接続時の破損を防ぐために接続荷重の高圧化には限度がある。また、半導体チップ側の電極と回路基板側の電極を合金化により直接接続する共晶接続や半田接続の場合には、電極間に不純物が存在すると十分な導通特性が得られないため、接続時に電極間から接着剤を完全に排除する必要がある。 In recent years, the number of pins of a semiconductor chip has increased, the chip thickness tends to decrease, and the connection load required per semiconductor chip has increased. On the other hand, there is a limit to increasing the connection load in order to prevent breakage during connection as the chip thickness decreases. In addition, in the case of eutectic connection or solder connection in which the electrode on the semiconductor chip side and the electrode on the circuit board side are directly connected by alloying, sufficient conduction characteristics cannot be obtained if there is an impurity between the electrodes. It is necessary to completely remove the adhesive from between the electrodes.
従って、半導体チップと回路基板を接続する接着剤には、接続時に粘度が十分低下する必要がある。また、排除性が良好であれば荷重を低圧化できるだけでなく、接続に要する時間を短縮したり温度を低温化することもできるため、半導体装置の製造にかかるコストを引き下げることができる。 Therefore, the adhesive for connecting the semiconductor chip and the circuit board needs to have a sufficiently reduced viscosity at the time of connection. In addition, if the rejection is good, not only can the load be reduced, but also the time required for connection can be shortened and the temperature can be lowered, so that the cost for manufacturing the semiconductor device can be reduced.
一般的に、フィルム状の接着剤を作製するためには、重量平均分子量が１０，０００以上の熱可塑性樹脂を配合している（例えば、特許文献２参照）。しかし、高分子量の樹脂を配合することによって加熱溶融時の粘度が十分低下せず、接続時の排除性が低下するため良好な接続信頼性が得られない。また、絶縁性無機フィラーを含まない樹脂成分のみの組成物では、溶融時の粘度が比較的低いが、硬化後の線膨張係数が半導体チップや回路基板に比べ大きく（３００〜５００ｐｐｍ／℃）耐熱性に劣るため、信頼性試験である吸湿リフロー性試験や冷熱サイクル試験等において半導体チップと回路基板間の電気的な接続を維持することができず，長期の接続信頼性に劣る。本発明は、接着剤による半導体チップと回路基板との電気的接続において、接続時の排除性が良好で、接続荷重が小さくチップ割れを防止できると共に接続信頼性に優れたフィルム状接着剤及びこれを用いた半導体装置を提供する。 Generally, in order to produce a film-like adhesive, a thermoplastic resin having a weight average molecular weight of 10,000 or more is blended (for example, see Patent Document 2). However, by blending a high molecular weight resin, the viscosity at the time of heating and melting does not sufficiently decrease, and the eliminability at the time of connection decreases, so that good connection reliability cannot be obtained. In addition, a composition containing only a resin component that does not contain an insulating inorganic filler has a relatively low viscosity at the time of melting, but its linear expansion coefficient after curing is larger than that of a semiconductor chip or circuit board (300 to 500 ppm / ° C.) Therefore, the electrical connection between the semiconductor chip and the circuit board cannot be maintained in a moisture absorption reflow test or a cooling cycle test, which is a reliability test, and the long-term connection reliability is poor. The present invention provides a film-like adhesive having excellent connection reliability, electrical connection between a semiconductor chip and a circuit board by an adhesive, excellent connection reliability, a small connection load and prevention of chip cracking, and excellent connection reliability. A semiconductor device using the above is provided.
本発明は、［１］５０〜２５０℃のいずれかの温度で粘度が２００Ｐａ・ｓ以下に達し、硬化物の２５℃〜２６０℃における平均線膨張係数が２００ｐｐｍ／℃以下であるフィルム状接着剤である。
これは、常温においてはフィルム状であって取り扱いが容易であり、加熱溶融時にペースト状の低粘度物となり十分な排除性あるいは回路充填性を有し、硬化後の線膨張係数が小さく耐熱性に優れるフィルム状接着剤を提供するものである。
また、本発明は、［２］下記（ａ）〜（ｄ）を必須成分とする上記［１］に記載のフィルム状接着剤である。
（ａ）重量平均分子量が１０，０００以下で、常温（２５℃）において固形である樹脂、（ｂ）絶縁性無機フィラー、（ｃ）エポキシ樹脂、（ｄ）硬化剤。
上記の発明は、上記［１］に記載の発明に加えて、汎用性の高い有機・無機材料からなるフィルム状接着剤を提供するものである。
また、本発明は、［３］（ｂ）絶縁性無機フィラーの充填量が４０〜８０重量％である上記［１］または上記［２］に記載のフィルム状接着剤である。
上記［３］に記載の発明は、上記［１］または上記［２］に記載の発明に加えて、適当な可とう性を有するフィルム状接着剤を提供するものである。
また、本発明は、［４］揮発分が１０重量％以下である上記［１］ないし上記［３］のいずれかに記載のフィルム状接着剤である。
上記［４］記載の発明は、上記［１］〜［３］のいずれかに記載の発明に加えて、硬化時のボイド発生が少ないフィルム状接着剤を提供するものである。
また、本発明は、［５］５０〜２５０℃のいずれかの温度で粘度が２００Ｐａ・ｓ以下である時間が３０秒間以上である上記［１］ないし上記［４］のいずれかに記載のフィルム状接着剤である。
上記［５］に記載の発明は、上記［１］〜［５］のいずれかに記載の発明に加えて、接続前にボイドの原因となる揮発分を低減することができ、また一つの基板に同時に多数のチップを接続できるフィルム状接着剤を提供するものである。また、本発明は、［６］上記［１］ないし上記［５］のいずれかに記載のフィルム状接着剤を用いて作製した半導体装置である。
上記［６］記載の発明は、従来よりも、低圧、短時間、低温での作製が可能であり、接続信頼性に優れる半導体装置を提供するものである。
The present invention is [1] a film adhesive in which the viscosity reaches 200 Pa · s or less at any temperature of 50 to 250 ° C., and the average linear expansion coefficient of the cured product at 25 to 260 ° C. is 200 ppm / ° C. or less. It is.
This is a film at room temperature and is easy to handle, becomes a paste-like low-viscosity product when heated and melted, has sufficient exclusion or circuit fillability, and has a low coefficient of linear expansion after curing and heat resistance. The present invention provides an excellent film adhesive.
Moreover, this invention is [2] The film adhesive as described in said [1] which has the following (a)-(d) as an essential component.
(A) A resin having a weight average molecular weight of 10,000 or less and solid at room temperature (25 ° C.), (b) an insulating inorganic filler, (c) an epoxy resin, and (d) a curing agent.
In addition to the invention described in [1], the above invention provides a film adhesive made of a highly versatile organic / inorganic material.
Moreover, this invention is a film adhesive as described in said [1] or [2] whose filling amount of [3] (b) insulating inorganic filler is 40 to 80 weight%.
The invention described in [3] provides a film adhesive having appropriate flexibility in addition to the invention described in [1] or [2].
[4] The film adhesive according to any one of [1] to [3], wherein the volatile content is 10% by weight or less.
The invention described in the above [4] provides a film-like adhesive that generates less voids during curing in addition to the invention described in any of the above [1] to [3].
[5] The film according to any one of [1] to [4], wherein the time at which the viscosity is 200 Pa · s or less at any temperature of 50 to 250 ° C. is 30 seconds or more. Adhesive.
In addition to the invention described in any one of [1] to [5] above, the invention described in [5] can reduce volatile components that cause voids before connection, and can be used as a single substrate. In addition, a film-like adhesive capable of simultaneously connecting a large number of chips is provided. The present invention also provides [6] a semiconductor device fabricated using the film adhesive according to any one of [1] to [5].
The invention described in [6] provides a semiconductor device that can be manufactured at a lower pressure, in a shorter time, and at a lower temperature than in the past, and has excellent connection reliability.
本発明によれば、重量平均分子量が１０，０００以下であって常温（２５℃）において固形である樹脂に適量の絶縁性無機フィラーとエポキシ樹脂、および硬化剤を含有させることにより、従来よりも溶融時の粘度が低く硬化後の耐熱性に優れる熱硬化性のフィルム状接着剤を作製することができる。また、本発明のフィルム状接着剤を用いた場合、従来よりも低圧、短時間、低温で半導体装置を作製することができ、この半導体装置は良好な接続信頼性を有する。 According to the present invention, the resin having a weight average molecular weight of 10,000 or less and solid at normal temperature (25 ° C.) contains an appropriate amount of an insulating inorganic filler, an epoxy resin, and a curing agent. A thermosetting film adhesive having a low viscosity at the time of melting and excellent heat resistance after curing can be produced. In addition, when the film adhesive of the present invention is used, a semiconductor device can be manufactured at a lower pressure, a shorter time, and a lower temperature than conventional ones, and this semiconductor device has good connection reliability.
本発明のフィルム状接着剤は、（ａ）重量平均分子量が１０，０００以下であって常温（２５℃）において固形である樹脂、（ｂ）絶縁性無機フィラー、（ｃ）エポキシ樹脂、（ｄ）硬化剤を必須成分とすることが好ましい。 The film-like adhesive of the present invention comprises (a) a resin having a weight average molecular weight of 10,000 or less and a solid at room temperature (25 ° C.), (b) an insulating inorganic filler, (c) an epoxy resin, (d ) It is preferable to use a curing agent as an essential component.
本発明において使用する（ａ）重量平均分子量が１０，０００以下で、常温（２５℃）において固形である樹脂としては、例えば、エポキシ樹脂、ポリイミド樹脂、ポリアミド樹脂、ポリカルボジイミド樹脂、フェノール樹脂、シアネートエステル樹脂、アクリル樹脂、ポリエステル樹脂、ポリエチレン樹脂、ポリエーテルスルホン樹脂、ポリエーテルイミド樹脂、ポリビニルアセタール樹脂、ウレタン樹脂、アクリルゴム等が挙げられ、その中でも、熱硬化性で耐熱性に優れるエポキシ樹脂、ポリイミド樹脂、シアネートエステル樹脂、ポリカルボジイミド樹脂等が好ましく、エポキシ樹脂、ポリイミド樹脂がより好ましい。これらは単独または２種以上の混合体として使用することもできる。 Examples of the resin (a) having a weight average molecular weight of 10,000 or less and solid at room temperature (25 ° C.) used in the present invention include epoxy resin, polyimide resin, polyamide resin, polycarbodiimide resin, phenol resin, and cyanate. Examples include ester resins, acrylic resins, polyester resins, polyethylene resins, polyethersulfone resins, polyetherimide resins, polyvinyl acetal resins, urethane resins, acrylic rubbers, etc. Among them, epoxy resins that are thermosetting and excellent in heat resistance, Polyimide resins, cyanate ester resins, polycarbodiimide resins and the like are preferable, and epoxy resins and polyimide resins are more preferable. These can be used alone or as a mixture of two or more.
本発明において使用する（ｂ）絶縁性無機フィラーとしては、例えば、シリカ、アルミナ、酸化チタン、カーボンブラック、マイカ等が挙げられ、その中でも、シリカ、アルミナ、酸化チタン等が好ましく、シリカ、アルミナがより好ましい。これらは単独または２種以上の混合体として使用することもできる。また、絶縁性無機フィラーの形状は増粘の影響が少ない球状のものが好ましい。同種の絶縁性無機フィラーを同重量部配合した場合、粒径の大きいもの程溶融時の粘度が低くなるが、本発明のフィルム状接着剤をフリップチップ実装用のフィルム状アンダーフィル材として使用する場合、絶縁性無機フィラーが電極に捕捉され電極間の電気的な導通を阻害するのを防ぐため、粒径は１０μｍ以下であることが好ましい。 Examples of the insulating inorganic filler (b) used in the present invention include silica, alumina, titanium oxide, carbon black, mica, etc. Among them, silica, alumina, titanium oxide and the like are preferable, and silica and alumina are preferable. More preferred. These can be used alone or as a mixture of two or more. Moreover, the shape of the insulating inorganic filler is preferably a spherical shape with little influence of thickening. When the same kind of insulating inorganic filler is blended in the same part by weight, the larger the particle size, the lower the viscosity at the time of melting, but the film-like adhesive of the present invention is used as a film-like underfill material for flip chip mounting. In this case, the particle diameter is preferably 10 μm or less in order to prevent the insulating inorganic filler from being captured by the electrodes and hindering electrical conduction between the electrodes.
本発明において使用する（ｃ）エポキシ樹脂としては、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ｏ−クレゾールノボラック型エポキシ樹脂、ビフェニル型エポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂、ナフタレン型エポキシ樹脂など、各種の多官能エポキシ樹脂化合物が挙げられる。これらは単独または２種以上の混合体として使用することもできる。また、エポキシ樹脂は、２５℃において液状、固形のいずれでも使用することができる。 Examples of the (c) epoxy resin used in the present invention include bisphenol A type epoxy resin, bisphenol F type epoxy resin, o-cresol novolac type epoxy resin, biphenyl type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin and the like. And various polyfunctional epoxy resin compounds. These can be used alone or as a mixture of two or more. The epoxy resin can be used in a liquid state or a solid state at 25 ° C.
本発明において使用する（ｄ）硬化剤としては、イミダゾール類、多価フェノール類、酸無水物類、アミン類、ヒドラジド類、ポリメルカプタン等が挙げられ、その中でも、保存安定性と硬化物の耐熱性に優れるイミダゾール類、多価フェノール類、酸無水物等が好ましく、イミダゾール類、多価フェノール類がより好ましい。これらは単独または２種以上の混合体として使用することもできる。また、接着剤の粘度が十分低下するまで硬化が開始しない程度のゲル化時間を有することが好ましい。硬化剤がイミダゾール類の場合、十分な可使時間とゲル化時間を有するものとして例えば、２Ｐ４ＭＨＺ、２ＰＨＺ、２ＭＡ−ＯＫ（四国化成工業株式会社製商品名）等が挙げられる。また、これらの硬化剤をポリウレタン系、ポリエステル系の高分子物質等で被覆してマイクロカプセル化したものは、可使時間が延長されるために好ましい。 Examples of the curing agent (d) used in the present invention include imidazoles, polyhydric phenols, acid anhydrides, amines, hydrazides, polymercaptan, etc. Among them, storage stability and heat resistance of the cured product are exemplified. Preferred are imidazoles, polyhydric phenols, acid anhydrides and the like, which are excellent in properties, and more preferred are imidazoles and polyhydric phenols. These can be used alone or as a mixture of two or more. Moreover, it is preferable to have a gelation time that does not start curing until the viscosity of the adhesive is sufficiently reduced. When the curing agent is an imidazole, 2P4MHZ, 2PHZ, 2MA-OK (trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.) and the like can be cited as examples having sufficient pot life and gelation time. In addition, those encapsulating these curing agents with polyurethane-based or polyester-based polymeric substances and the like and microencapsulated are preferable because the pot life is extended.
本発明における（ａ）重量平均分子量が１０，０００以下であって常温（２５℃）において固形である樹脂の配合量は、（ａ）重量平均分子量が１０，０００以下であって常温（２５℃）において固形である樹脂、（ｂ）絶縁性無機フィラー、（ｃ）エポキシ樹脂の総量１００重量部に対して、５〜８０重量部とすることが好ましく、１０〜６０重量部とすることがより好ましく、２０〜５０重量部とすることが特に好ましい。この配合量が、５重量部未満では、フィルム形成が困難となる傾向があり、８０重量部を超えると、硬化後の線膨張係数が大きくなる傾向がある。 In the present invention, the blending amount of the resin (a) having a weight average molecular weight of 10,000 or less and solid at normal temperature (25 ° C.) is (a) having a weight average molecular weight of 10,000 or less and normal temperature (25 ° C. 5) to 80 parts by weight, and more preferably 10 to 60 parts by weight with respect to 100 parts by weight of the total amount of the resin, (b) insulating inorganic filler, and (c) epoxy resin. It is particularly preferably 20 to 50 parts by weight. If the blending amount is less than 5 parts by weight, film formation tends to be difficult, and if it exceeds 80 parts by weight, the linear expansion coefficient after curing tends to increase.
本発明における（ｂ）絶縁性無機フィラーの配合量は、（ａ）重量平均分子量が１０，０００以下であって常温（２５℃）において固形である樹脂、（ｂ）絶縁性無機フィラー、（ｃ）エポキシ樹脂の総量１００重量部に対して、１０〜９０重量部とすることが好ましく、３０〜８５重量部とすることがより好ましく、４０〜８０重量部とすることが特に好ましい。この配合量が、１０重量部未満では、硬化後の線膨張係数が大きくなる傾向があり、９０重量部を超えると、溶融時の粘度が上昇する傾向があり、またフィルムの可とう性が低下し脆くなる傾向がある。 The blending amount of the (b) insulating inorganic filler in the present invention is as follows: (a) a resin having a weight average molecular weight of 10,000 or less and solid at room temperature (25 ° C.), (b) an insulating inorganic filler, (c ) It is preferably 10 to 90 parts by weight, more preferably 30 to 85 parts by weight, and particularly preferably 40 to 80 parts by weight with respect to 100 parts by weight of the total epoxy resin. If the blending amount is less than 10 parts by weight, the linear expansion coefficient after curing tends to increase, and if it exceeds 90 parts by weight, the viscosity at the time of melting tends to increase, and the flexibility of the film decreases. Tend to be brittle.
本発明における（ｃ）エポキシ樹脂の配合量は、（ａ）重量平均分子量が１０，０００以下であって常温（２５℃）において固形である樹脂、（ｂ）絶縁性無機フィラー、（ｃ）エポキシ樹脂の総量１００重量部に対して、５〜６０重量部とすることが好ましく、１０〜６０重量部とすることがより好ましく、２０〜６０重量部とすることが特に好ましい。この配合量が、２０重量部未満では、硬化物の耐熱性が低下する傾向があり、６０重量部を超えると、硬化物の線膨張係数が大きくなる傾向がある。なお、（ａ）重量平均分子量が１０，０００以下であって常温（２５℃）において固形である樹脂がエポキシ樹脂の場合は、（ｃ）エポキシ樹脂に含める。 The blending amount of the (c) epoxy resin in the present invention is (a) a resin having a weight average molecular weight of 10,000 or less and a solid at room temperature (25 ° C.), (b) an insulating inorganic filler, and (c) an epoxy. It is preferably 5 to 60 parts by weight, more preferably 10 to 60 parts by weight, and particularly preferably 20 to 60 parts by weight with respect to 100 parts by weight of the total resin. If the blending amount is less than 20 parts by weight, the heat resistance of the cured product tends to decrease, and if it exceeds 60 parts by weight, the linear expansion coefficient of the cured product tends to increase. In the case where (a) the resin having a weight average molecular weight of 10,000 or less and solid at room temperature (25 ° C.) is an epoxy resin, it is included in (c) the epoxy resin.
本発明における（ｄ）硬化剤の配合量は、硬化剤の種類により異なるが、硬化剤がイミダゾール類の場合には、（ｃ）エポキシ樹脂１００重量部に対して、０．０１〜５０重量部とすることが好ましく、０．１〜２０重量部とすることがより好ましく、１〜１０重量部とすることが特に好ましい。この配合量が、０．０１重量部未満では、半導体チップと回路基板の一般的な接続条件において硬化不足となる傾向があり、５０重量部を超えると、接着剤の硬化物物性を低下させる傾向がある。 The blending amount of the (d) curing agent in the present invention varies depending on the type of the curing agent, but when the curing agent is an imidazole, 0.01 to 50 parts by weight with respect to 100 parts by weight of the (c) epoxy resin. The content is preferably 0.1 to 20 parts by weight, more preferably 1 to 10 parts by weight. If the blending amount is less than 0.01 parts by weight, curing tends to be insufficient under general connection conditions between the semiconductor chip and the circuit board. If the blending amount exceeds 50 parts by weight, the cured product physical properties of the adhesive tend to be lowered. There is.
本発明のフィルム状接着剤には、上記必須成分以外に、シラン系またはチタン系のカップリング剤を使用することができる。この使用量としては、（ａ）重量平均分子量が１０，０００以下であって常温（２５℃）において固形である樹脂、（ｂ）絶縁性無機フィラー、（ｃ）エポキシ樹脂の総量１００重量に対して、０．１〜１０重量部とすることが好ましい。 In addition to the above essential components, a silane-based or titanium-based coupling agent can be used for the film adhesive of the present invention. The amount used is as follows: (a) a resin having a weight average molecular weight of 10,000 or less and a solid at room temperature (25 ° C.), (b) an insulating inorganic filler, and (c) 100 wt. And preferably 0.1 to 10 parts by weight.
また、フィルム状接着剤に可とう性あるいは粘着性を付与する等の目的で液状の樹脂を使用することができる。この使用量としては（ａ）重量平均分子量が１０，０００以下であって常温（２５℃）において固形である樹脂、（ｂ）絶縁性無機フィラー、（ｃ）エポキシ樹脂の総量１００重量部に対して、５〜５０重量部とすることが好ましい。また、本発明のフィルム状接着剤には、導電性粒子を使用することができ，この使用量としては、０．１〜１０体積％である。 A liquid resin can be used for the purpose of imparting flexibility or tackiness to the film adhesive. The amount used is based on (a) a resin having a weight average molecular weight of 10,000 or less and solid at room temperature (25 ° C.), (b) an insulating inorganic filler, and (c) 100 parts by weight of the total amount of epoxy resin. Thus, the amount is preferably 5 to 50 parts by weight. Moreover, electroconductive particle can be used for the film adhesive of this invention, As this usage-amount, it is 0.1-10 volume%.
また、フィルム状接着剤のフィルム形成性を向上させたり耐熱性を付与する等の目的で、粘度低下を妨げない程度の量の分子量１０，０００以上の樹脂を配合することができる。 In addition, for the purpose of improving the film-forming property of the film-like adhesive or imparting heat resistance, a resin having a molecular weight of 10,000 or more can be blended in such an amount that does not hinder the decrease in viscosity.
以上、説明した本発明のフィルム状接着剤は、例えば図１〜３に示すように、半導体チップを回路基板に固定し電気的に接続するフィルム状のアンダーフィル材またはダイボンド材等として使用することができ、特にフリップチップ実装の短時間接続が可能な超音波接合等において有効である。これらは、図４に示すように一つの回路基板に同時に多数の半導体チップを接続することができる。また、図５に示すようにトランスファー成形が不要なシート状の半導体用封止材等として、あるいはウエハレベルＣＳＰパッケージの保護膜、応力緩和層等として用いることもできる。 As described above, the film-like adhesive of the present invention described above is used as a film-like underfill material or die-bonding material for fixing and electrically connecting a semiconductor chip to a circuit board as shown in FIGS. In particular, it is effective in ultrasonic bonding or the like that can be connected in a short time by flip chip mounting. As shown in FIG. 4, these can simultaneously connect a large number of semiconductor chips to one circuit board. Further, as shown in FIG. 5, it can be used as a sheet-like semiconductor sealing material that does not require transfer molding, or as a protective film, a stress relaxation layer, or the like of a wafer level CSP package.
以下、実施例により本発明を具体的に説明する。 Hereinafter, the present invention will be described specifically by way of examples.
（実施例１）
重量平均分子量が１０，０００以下であって常温（２５℃）において固形である樹脂として分子量が１，６００のビスフェノールＡ型エポキシ樹脂（ジャパンエポキシレジン株式会社製：ＥＰ１００４）１００重量部とシランカップリング剤（東レ・ダウコーニング・シリコーン株式会社製：ＳＨ６０４０）３重量部をメチルエチルケトンに溶解し、得られた樹脂ワニス中に平均粒径２μｍの球状シリカ（三菱レイヨン株式会社製：ＱＳ２）を１５０重量部添加し、３０分混練した。これに硬化剤としてイミダゾール（四国化成工業株式会社製：２Ｐ４ＭＨＺ）を５重量部添加し、均一に攪拌した後、減圧脱泡して接着剤ワニスを得た。この接着剤ワニスを離型処理された５０μｍ厚のＰＥＴ（ポリエチレンテレフタレート）フィルム上に塗工し、７０℃にて１０分間乾燥してメチルエチルケトンを除去し、５０μｍ厚のフィルム状接着剤を作製した。
Example 1
Silane coupling with 100 parts by weight of bisphenol A type epoxy resin (EP1004, manufactured by Japan Epoxy Resin Co., Ltd.) having a weight average molecular weight of 10,000 or less and a solid resin at room temperature (25 ° C.). 150 parts by weight of spherical silica (Mitsubishi Rayon Co., Ltd .: QS2) having an average particle size of 2 μm was dissolved in methyl ethyl ketone in 3 parts by weight of an agent (Toray Dow Corning Silicone Co., Ltd .: SH6040). Added and kneaded for 30 minutes. To this was added 5 parts by weight of imidazole (manufactured by Shikoku Kasei Kogyo Co., Ltd .: 2P4MHZ) as a curing agent, and after uniform stirring, degassed under reduced pressure to obtain an adhesive varnish. This adhesive varnish was coated on a 50 μm-thick PET (polyethylene terephthalate) film which had been subjected to a release treatment, and dried at 70 ° C. for 10 minutes to remove methyl ethyl ketone, thereby producing a 50 μm-thick film adhesive.
（実施例２）
分子量が１，６００のエポキシ樹脂を分子量３９０の液状エポキシ樹脂（ジャパンエポキシレジン株式会社製：ＥＰ８２８）２０重量部と分子量が１，６００のエポキシ樹脂８０重量部に置き換えた以外は、実施例１と全て同じ条件で行いフィルム状接着剤を作製した。
(Example 2)
Example 1 except that the epoxy resin having a molecular weight of 1,600 was replaced with 20 parts by weight of a liquid epoxy resin having a molecular weight of 390 (EP828, manufactured by Japan Epoxy Resin Co., Ltd.) and 80 parts by weight of an epoxy resin having a molecular weight of 1,600. All were performed on the same conditions, and the film adhesive was produced.
（実施例３）
分子量が１，６００のエポキシ樹脂を分子量３９０の液状エポキシ樹脂２０重量部と分子量が１，６００のエポキシ樹脂６０重量部とｏ−クレゾールノボラック型エポキシ樹脂（住友化学工業株式会社製：ＥＳＣＮ１９５ＸＬ）２０重量部に置き換えた以外は、実施例１と全て同じ条件で行いフィルム状接着剤を作製した。
Example 3
An epoxy resin having a molecular weight of 1,600, 20 parts by weight of a liquid epoxy resin having a molecular weight of 390, 60 parts by weight of an epoxy resin having a molecular weight of 1,600, and 20 parts by weight of an o-cresol novolac type epoxy resin (manufactured by Sumitomo Chemical Co., Ltd .: ESCN195XL) A film-like adhesive was produced under the same conditions as in Example 1 except that the part was replaced with a part.
（実施例４）
分子量が１，６００のエポキシ樹脂を分子量８，１００のアクリル樹脂（ジョンソンポリマー株式会社製：ＪＣ６１１）７０重量部と分子量３９０の液状エポキシ樹脂３０重量部に置き換えた以外は、実施例１と全て同じ条件で行いフィルム状接着剤を作製した。
Example 4
The same as Example 1 except that the epoxy resin having a molecular weight of 1,600 was replaced with 70 parts by weight of an acrylic resin having a molecular weight of 8,100 (manufactured by Johnson Polymer Co., Ltd .: JC611) and 30 parts by weight of a liquid epoxy resin having a molecular weight of 390. A film adhesive was produced under the conditions.
（実施例５）
分子量が１，６００のエポキシ樹脂を分子量が２，９００のビスフェノールＡ型エポキシ樹脂（ジャパンエポキシレジン株式会社製：ＥＰ１００７）２０重量部と分子量３９０の液状エポキシ樹脂２０重量部と分子量が１，６００のエポキシ樹脂６０重量部に置き換え、球状シリカを７０重量部とした以外は、実施例１と全て同じ条件で行いフィルム状接着剤を作製した。
(Example 5)
An epoxy resin having a molecular weight of 1,600 is 20 parts by weight of a bisphenol A type epoxy resin having a molecular weight of 2,900 (manufactured by Japan Epoxy Resin Co., Ltd .: EP1007), 20 parts by weight of a liquid epoxy resin having a molecular weight of 390, and a molecular weight of 1,600. A film-like adhesive was prepared in the same manner as in Example 1 except that 60 parts by weight of epoxy resin was used and that 70 parts by weight of spherical silica was used.
（実施例６）
分子量が１，６００のエポキシ樹脂を分子量３９０の液状エポキシ樹脂６０重量部と分子量が１，６００のエポキシ樹脂４０重量部に置き換え、球状シリカを３００重郎部とした以外は、実施例１と全て同じ条件で行いフィルム状接着剤を作製した。
(Example 6)
Except that the epoxy resin having a molecular weight of 1,600 was replaced with 60 parts by weight of a liquid epoxy resin having a molecular weight of 390 and 40 parts by weight of an epoxy resin having a molecular weight of 1,600, and spherical silica was changed to 300 parts by weight, all the same as Example 1. A film adhesive was produced under the conditions.
（比較例１）
分子量が１，６００のエポキシ樹脂を分子量３９０の液状エポキシ樹脂７０重量部と分子量約５０，０００のフェノキシ樹脂（ユニオンカーバイド株式会社製：ＰＫＨＣ）３０重量部に置き換えた以外は、実施例１と全て同じ条件で行いフィルム状接着剤を作製した。
(Comparative Example 1)
Except for replacing the epoxy resin having a molecular weight of 1,600 with 70 parts by weight of a liquid epoxy resin having a molecular weight of 390 and 30 parts by weight of a phenoxy resin having a molecular weight of about 50,000 (PKHC manufactured by Union Carbide Co., Ltd.) A film-like adhesive was produced under the same conditions.
（比較例２）
分子量が１，６００のエポキシ樹脂を分子量３９０の液状エポキシ樹脂６０重量部と分子量約５０，０００のフェノキシ樹脂４０重量部に置き換えた以外は、実施例１と全て同じ条件で行いフィルム状接着剤を作製した。
(Comparative Example 2)
Except that the epoxy resin with a molecular weight of 1,600 was replaced with 60 parts by weight of a liquid epoxy resin with a molecular weight of 390 and 40 parts by weight of a phenoxy resin with a molecular weight of about 50,000, the film adhesive was carried out under the same conditions as in Example 1. Produced.
（比較例３）
分子量が１，６００のエポキシ樹脂を分子量３９０の液状エポキシ樹脂７０重量部と分子量約７０，０００のポリビニルアセタール樹脂（電気化学工業株式会社製：ＰＶＢ−３０００Ｋ）３０重量部に置き換えた以外は、実施例１と全て同じ条件で行いフィルム状接着剤を作製した。
(Comparative Example 3)
Except for replacing the epoxy resin having a molecular weight of 1,600 with 70 parts by weight of a liquid epoxy resin having a molecular weight of 390 and 30 parts by weight of a polyvinyl acetal resin having a molecular weight of about 70,000 (manufactured by Denki Kagaku Kogyo Co., Ltd .: PVB-3000K). A film adhesive was prepared under the same conditions as in Example 1.
（比較例４）
球状シリカの配合量を５０重量部とした以外は、実施例１と全て同じ条件で行いフィルム状接着剤を作製した。
(Comparative Example 4)
A film adhesive was produced under the same conditions as in Example 1 except that the amount of spherical silica was changed to 50 parts by weight.
（比較例５）
球状シリカの配合量を５００重量部とした以外は、実施例１と全て同じ条件で行いフィルム状接着剤を作製した。
(Comparative Example 5)
A film-like adhesive was prepared in the same manner as in Example 1 except that the amount of spherical silica was changed to 500 parts by weight.
実施例及び比較例において、特性の評価は以下の方法により行い、その結果を接着剤の配合組成と共に表１に示した。
（フィルム形成性）
７０℃にて１０分間乾燥する際に接着剤ワニスが流動することなくフィルム状の接着剤が形成され、また９０°曲げに対してクラックが発生しないことを観察した。乾燥中に流動することなく、曲げに対してクラックが発生しないものを「○」とし、流動またはクラックが発生するものを「×」として評価した。
（溶融粘度測定）
ずり粘弾性測定装置（レオメトリック・サイエンティフィック・エフ・イー株式会社製）を用い直径７．９ｍｍの平行板を使用して、サンプル厚み０．５から１．０ｍｍで周波数１０Ｈｚにおいて１５０℃に設定した時のせん断粘度を測定した。また、このとき粘度が２００Ｐａ・ｓ以下である時間を測定した。
（平均線膨張係数測定）
作製したフィルム状接着剤を２００℃にて１時間硬化し、ＴＭＡ測定装置（セイコーインスツルメンツ株式会社製）を用いて昇温速度５℃／分で２５〜２６０℃における平均線膨張係数を測定した。
（接続性）
回路基板（ガラスエポキシ基板、サイズ２５ｍｍ角、厚さ０．８ｍｍ、電極高さ２０μｍ）にフィルム状接着剤を仮付けし、半導体チップ（サイズ１０ｍｍ角、厚さ０．５５ｍｍ、バンプ高さ３０μｍ、バンプ数１８４個、保護膜窒化珪素）を位置合わせして、フリップチップボンディング装置（ミスズＦＡ株式会社製）で接続を行った。
（冷熱サイクル試験）
フィルム状接着剤を用いて半導体チップと回路基板を接続した半導体装置を１５０℃のオーブン中で２時間加熱し接着剤を完全に硬化させた後、冷熱サイクル試験機（−５５〜１２５℃、間隔３０分）に投入し一端子当りの接続抵抗値が１０ｍΩ以上となるサイクル数を求めた。
In the examples and comparative examples, the characteristics were evaluated by the following method, and the results are shown in Table 1 together with the composition of the adhesive.
(Film formability)
When drying at 70 ° C. for 10 minutes, it was observed that a film-like adhesive was formed without flowing of the adhesive varnish, and no crack was generated with respect to 90 ° bending. Evaluation was made as “◯” when no cracking occurred during bending without flowing during drying, and “X” when flow or cracking occurred.
(Melt viscosity measurement)
Using a parallel plate with a diameter of 7.9 mm using a shear viscoelasticity measuring device (Rheometric Scientific F.E. Co., Ltd.), a sample thickness of 0.5 to 1.0 mm and a frequency of 10 Hz to 150 ° C. The shear viscosity when set was measured. At this time, the time during which the viscosity was 200 Pa · s or less was measured.
(Average linear expansion coefficient measurement)
The produced film adhesive was cured at 200 ° C. for 1 hour, and an average coefficient of linear expansion at 25 to 260 ° C. was measured at a heating rate of 5 ° C./min using a TMA measuring apparatus (manufactured by Seiko Instruments Inc.).
(Connectivity)
A film adhesive is temporarily attached to a circuit board (glass epoxy board, size 25 mm square, thickness 0.8 mm, electrode height 20 μm), and a semiconductor chip (size 10 mm square, thickness 0.55 mm, bump height 30 μm, 184 bumps, protective film silicon nitride) were aligned and connected by a flip chip bonding apparatus (manufactured by Misuzu FA Co., Ltd.).
(Cooling cycle test)
A semiconductor device in which a semiconductor chip and a circuit board are connected using a film adhesive is heated in an oven at 150 ° C. for 2 hours to completely cure the adhesive, and then a thermal cycle tester (−55 to 125 ° C., interval) 30 minutes), and the number of cycles at which the connection resistance value per terminal is 10 mΩ or more was determined.
表１の実施例１〜６に示すように、重量平均分子量が１０，０００以下であって常温（２５℃）において固形である樹脂を用い球状シリカの充填量が４０〜８０重量％である場合には、溶融時の粘度が２００Ｐａ・ｓ以下に達し、かつ硬化後の平均線膨張係数が２００ｐｐｍ以下となるフィルム状接着剤が得られた。実施例１の粘度測定結果を図６に示した。 As shown in Examples 1 to 6 in Table 1, when the weight-average molecular weight is 10,000 or less and the solid silica is used at room temperature (25 ° C.), the amount of spherical silica is 40 to 80% by weight. A film-like adhesive having a viscosity at melting of 200 Pa · s or less and an average linear expansion coefficient after curing of 200 ppm or less was obtained. The viscosity measurement result of Example 1 is shown in FIG.
また、このフィルム状接着剤を用いて半導体チップと回路基板を接続した場合、分子量が１０，０００以上の樹脂を用いた従来のフィルム状接着剤に比べ、低荷重、短時間で導通が可能であり、その半導体装置は冷熱サイクル試験において良好な接続信頼性を示した。一方、比較例１では、フィルム形成材として分子量約５０，０００のフェノキシ樹脂を用い低粘度化のために液状のエポキシ樹脂を多量配合しているが、粘着性が強く良好なフィルム形成性が得られない。また、比較例２では、比較例１でのフィルム形成性を改善する目的でフェノキシ樹脂を増加し液状エポキシ樹脂を減少しているが溶融時の粘度が高い。比較例２の粘度測定結果を図７に示した。比較例３では、比較例１でのフィルム形成性を改善する目的でフェノキシ樹脂の代わりに分子量約７０，０００のポリビニルアセタール樹脂を使用しているが溶融時の粘度が高い。 In addition, when a semiconductor chip and a circuit board are connected using this film adhesive, conduction is possible in a shorter time and with a lower load than conventional film adhesives using a resin having a molecular weight of 10,000 or more. The semiconductor device showed good connection reliability in the thermal cycle test. On the other hand, in Comparative Example 1, a phenoxy resin having a molecular weight of about 50,000 is used as a film forming material, and a large amount of a liquid epoxy resin is blended to reduce the viscosity. I can't. In Comparative Example 2, the phenoxy resin is increased and the liquid epoxy resin is decreased for the purpose of improving the film formability in Comparative Example 1, but the viscosity at the time of melting is high. The viscosity measurement result of Comparative Example 2 is shown in FIG. In Comparative Example 3, a polyvinyl acetal resin having a molecular weight of about 70,000 is used instead of the phenoxy resin for the purpose of improving the film formability in Comparative Example 1, but the viscosity at the time of melting is high.
比較例４では、絶縁性無機フィラーの配合量を減らすことによって溶融時の粘度が低いが、硬化後の線膨張係数が大きく、冷熱サイクル試験において十分な接続信頼性が得られない。比較例５では、絶縁性無機フィラーを高充填することにより、硬化後の線膨張係数は小さいが、溶融時に粘度が十分低下せず導通に要する荷重が高い。 In Comparative Example 4, although the viscosity at the time of melting is low by reducing the blending amount of the insulating inorganic filler, the linear expansion coefficient after curing is large, and sufficient connection reliability cannot be obtained in the thermal cycle test. In Comparative Example 5, the linear expansion coefficient after curing is small by high filling with the insulating inorganic filler, but the viscosity is not sufficiently lowered at the time of melting and the load required for conduction is high.
１．半導体チップ
２．突起電極
３．アンダーフィルフィルム
４．回路基板
５．電極
６．電極パッド
９．接続ツール
１０．加熱装置
１１．シート状封止材
1. Semiconductor chip Projection electrode Underfill film 4. Circuit board 5. Electrode 6. 8. Electrode pad Connection tool 10. Heating device 11. Sheet-like sealing material
Claims (8)
前記フィルム状アンダーフィル材が、（ａ）重量平均分子量が１０，０００以下で、常温（２５℃）において固形であるアクリル樹脂又はエポキシ樹脂、（ｂ）絶縁性無機フィラー、（ｃ）２５℃において液状であるエポキシ樹脂及び（ｄ）硬化剤を含有し、かつ、導電性粒子を含有せず、
（ｄ）硬化剤が、イミダゾール類であり、
（ａ）重量平均分子量が１０，０００以下で、常温（２５℃）において固形であるアクリル樹脂又はエポキシ樹脂の配合量が、（ａ）重量平均分子量が１０，０００以下で、常温（２５℃）において固形であるアクリル樹脂又はエポキシ樹脂、（ｂ）絶縁性無機フィラー及び（ｃ）２５℃において液状であるエポキシ樹脂の総量１００重量部に対して、１０〜６０重量部であり、
（ｂ）絶縁性無機フィラーの配合量が、（ａ）重量平均分子量が１０，０００以下で、常温（２５℃）において固形であるアクリル樹脂又はエポキシ樹脂、（ｂ）絶縁性無機フィラー及び（ｃ）２５℃において液状であるエポキシ樹脂の総量１００重量部に対して、４０〜８０重量部であり、
前記フィルム状アンダーフィル材の１５０℃における最低溶融粘度が２００Ｐａ・ｓ以下であり、
前記フィルム状アンダーフィル材を２００℃にて１時間硬化させて得られる硬化物の昇温速度５℃／分での２５℃〜２６０℃における平均線膨張係数が２００ｐｐｍ／℃以下である、
半導体装置の製造方法
（ただし、
（ａ）重量平均分子量が１０，０００以下で、常温（２５℃）において固形であるアクリル樹脂又はエポキシ樹脂の配合量が、（ａ）重量平均分子量が１０，０００以下で、常温（２５℃）において固形であるアクリル樹脂又はエポキシ樹脂、（ｂ）絶縁性無機フィラー及び（ｃ）２５℃において液状であるエポキシ樹脂の総量１００重量部に対して、２０〜５０重量部であり、且つ、
（ｂ）絶縁性無機フィラーの配合量が、（ａ）重量平均分子量が１０，０００以下で、常温（２５℃）において固形であるアクリル樹脂又はエポキシ樹脂、（ｂ）絶縁性無機フィラー及び（ｃ）２５℃において液状であるエポキシ樹脂の総量１００重量部に対して、４０〜６０重量部である、前記アンダーフィル材を使用する場合を除く。）。 A method of manufacturing a semiconductor device, using a film-like underfill material, and electrically connecting an electrode of a semiconductor chip and an electrode of a circuit board facing each other,
The film-like underfill material is (a) an acrylic resin or epoxy resin having a weight average molecular weight of 10,000 or less and solid at room temperature (25 ° C.), (b) an insulating inorganic filler, and (c) at 25 ° C. Containing a liquid epoxy resin and (d) a curing agent, and no conductive particles,
(D) the curing agent is an imidazole,
(A) The weight average molecular weight is 10,000 or less and the blending amount of the acrylic resin or epoxy resin which is solid at normal temperature (25 ° C.) is (a) the weight average molecular weight is 10,000 or less and normal temperature (25 ° C.). 10 to 60 parts by weight with respect to 100 parts by weight of the total amount of acrylic resin or epoxy resin that is solid in (b) insulating inorganic filler and (c) epoxy resin that is liquid at 25 ° C.
(B) The blending amount of the insulating inorganic filler is (a) an acrylic resin or epoxy resin having a weight average molecular weight of 10,000 or less and solid at room temperature (25 ° C.), (b) the insulating inorganic filler and (c ) 40 to 80 parts by weight with respect to 100 parts by weight of the total amount of epoxy resin that is liquid at 25 ° C.,
The minimum melt viscosity at 150 ° C. of the film-like underfill material is 200 Pa · s or less,
The average linear expansion coefficient at 25 ° C. to 260 ° C. at a temperature increase rate of 5 ° C./min of a cured product obtained by curing the film-like underfill material at 200 ° C. for 1 hour is 200 ppm / ° C. or less.
Manufacturing method of semiconductor device
(However,
(A) The weight average molecular weight is 10,000 or less and the blending amount of the acrylic resin or epoxy resin which is solid at normal temperature (25 ° C.) is (a) the weight average molecular weight is 10,000 or less and normal temperature (25 ° C.). 20 to 50 parts by weight with respect to 100 parts by weight of the total amount of the acrylic resin or epoxy resin that is solid in (b) insulating inorganic filler and (c) epoxy resin that is liquid at 25 ° C., and
(B) The blending amount of the insulating inorganic filler is (a) an acrylic resin or epoxy resin having a weight average molecular weight of 10,000 or less and solid at room temperature (25 ° C.), (b) the insulating inorganic filler and (c ) Except when the underfill material is 40-60 parts by weight with respect to 100 parts by weight of the total amount of epoxy resin that is liquid at 25 ° C. )
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| JP4537555B2 (en) * | 2000-09-11 | 2010-09-01 | 新日鐵化学株式会社 | Semiconductor package manufacturing method and semiconductor package |
| JP5134747B2 (en) * | 2000-11-28 | 2013-01-30 | 日立化成工業株式会社 | Adhesive film and semiconductor device |
| JP5274744B2 (en) * | 2002-09-30 | 2013-08-28 | 日立化成株式会社 | Film adhesive and semiconductor device using the same |
-
2011
- 2011-10-24 JP JP2011233035A patent/JP5626179B2/en not_active Expired - Fee Related
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