WO2017155117A1 - 半導体センサチップ実装用接着剤及び半導体センサ - Google Patents
半導体センサチップ実装用接着剤及び半導体センサ Download PDFInfo
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- WO2017155117A1 WO2017155117A1 PCT/JP2017/009816 JP2017009816W WO2017155117A1 WO 2017155117 A1 WO2017155117 A1 WO 2017155117A1 JP 2017009816 W JP2017009816 W JP 2017009816W WO 2017155117 A1 WO2017155117 A1 WO 2017155117A1
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Images
Classifications
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- H01L23/48—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor
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- 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
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- 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
- 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
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
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- C—CHEMISTRY; METALLURGY
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
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- C09J171/02—Polyalkylene oxides
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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
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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
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Abstract
Description
本発明に係る半導体センサチップ実装用接着剤(以下、接着剤と記載することがある)は、半導体センサチップの実装に用いられる接着剤である。本発明に係る接着剤は、シリコーン樹脂とスペーサとを含む。
F:スペーサが10%圧縮変形したときの荷重値(N)
S:スペーサが10%圧縮変形したときの圧縮変位(mm)
R:スペーサの半径(mm)
L1:負荷を与えるときの原点用荷重値から反転荷重値に至るまでの圧縮変位
L2:負荷を解放するときの反転荷重値から原点用荷重値に至るまでの除荷変位
本発明に係る半導体センサは、第1の部材と、第2の部材である半導体センサチップと、第1,第2の部材を接着している接着層とを備える。本発明に係る半導体センサでは、上記接着層が、上記接着剤の硬化物により形成されている。
シリコーンオリゴマーの作製:
温浴槽内に設置した100mlのセパラブルフラスコに、1,3-ジビニルテトラメチルジシロキサン1重量部と、0.5重量%p-トルエンスルホン酸水溶液20重量部とを入れた。40℃で1時間撹拌した後、炭酸水素ナトリウム0.05重量部を添加した。その後、ジメトキシメチルフェニルシラン10重量部、ジメチルジメトキシシラン49重量部、トリメチルメトキシシラン0.6重量部、及びメチルトリメトキシシラン3.6重量部を添加し、1時間撹拌を行った。その後、10重量%水酸化カリウム水溶液1.9重量部を添加して、85℃まで昇温してアスピレーターで減圧しながら、10時間撹拌、反応を行った。反応終了後、常圧に戻し40℃まで冷却して、酢酸0.2重量部を添加し、12時間以上分液漏斗内で静置した。二層分離後の下層を取り出して、エバポレーターにて精製することでシリコーンオリゴマーを得た。
得られたシリコーンオリゴマー30重量部に、tert-ブチル-2-エチルペルオキシヘキサノアート(重合開始剤、日油社製「パーブチルO」)0.5重量部を溶解させた溶解液Aを用意した。また、イオン交換水150重量部に、ラウリル硫酸トリエタノールアミン塩の40重量%水溶液(乳化剤)0.8重量部と、ポリビニルアルコール(重合度:約2000、けん化度:86.5~89モル%、日本合成化学社製「ゴーセノールGH-20」)の5重量%水溶液80重量部とを混合して、水溶液Bを用意した。温浴槽中に設置したセパラブルフラスコに、上記溶解液Aを入れた後、上記水溶液Bを添加した。その後、Shirasu Porous Glass(SPG)膜(細孔平均径約20μm)を用いることで、乳化を行った。その後、85℃に昇温して、9時間重合を行った。重合後の粒子の全量を遠心分離により水洗浄した後、分級操作を行ってシリコーン粒子を得た。
温浴槽内に設置した500mlのセパラブルフラスコに、得られたシリコーン粒子6.5重量部と、ヘキサデシルトリメチルアンモニウムブロミド0.6重量部と、蒸留水240重量部と、メタノール120重量部とを入れた。40℃で1時間攪拌した後、ジビニルベンゼン3.0重量部とスチレン0.5重量部とを添加して、75℃まで昇温して0.5時間攪拌を行った。その後、2,2’-アゾビス(イソ酪酸)ジメチル0.4重量部を入れて8時間攪拌、反応を行った。重合後の粒子の全量を遠心分離により水洗浄して、スペーサ1を得た。得られたスペーサ1では、平均粒子径は20.5μm、粒子径のCV値は3.5%であった。
シリコーンオリゴマーの代わりに両末端アクリルシリコーンオイル(信越化学工業社製「X-22-2445」)を用いたこと以外はスペーサ1の作製と同様にして、スペーサ2を得た。得られたスペーサ2では、平均粒子径は20.3μm、粒子径のCV値は3.6%であった。
エチレングリコールジメタクリレート100gと、イソボルニルアクリレート800gと、シクロヘキシルメタクリレート100gと、過酸化ベンゾイル35gとを混合し、均一に溶解させて、モノマー混合液を得た。1重量%ポリビニルアルコール水溶液5kgを作製し、反応釜に入れた。この反応釜の中に上記モノマー混合液を更に入れ、2~4時間攪拌することで、モノマー混合液の液滴が所定の粒子径になるように、粒子径を調整した。この後90℃の窒素雰囲気下で9時間反応を行い、スペーサ3を得た。得られたスペーサ3を熱水にて数回洗浄した後、分級操作を行った。得られたスペーサ3では、平均粒子径は20.1μm、粒子径のCV値は3.1%であった。
市販の20μmのシリカ粒子「ミクロパールSI」(積水化学工業社製)
テトラメチロールメタン500gと、ジビニルベンゼン500gと、過酸化ベンゾイル20gとを混合し、均一に溶解させてモノマー混合液を得た。1重量%ポリビニルアルコール水溶液5kgを作製し、反応釜に入れた。この反応釜の中に上記モノマー混合液を更に入れ、2~4時間攪拌することで、モノマー混合液の液滴が所定の粒子径になるように、粒子径を調整した。この後85℃の窒素雰囲気下で10時間反応を行い、スペーサBを得た。得られたスペーサBを熱水にて数回洗浄した後、分級操作を行った。得られたスペーサBでは、平均粒子径は19.8μm、粒子径のCV値は3.5%であった。
ポリテトラメチレングリコールジアクリレート970gと、テトラメチロールメタンテトラアクリレート30gと、過酸化ベンゾイル39gとを混合し、均一に溶解させてモノマー混合液を得た。1重量%ポリビニルアルコール水溶液5kgを作製し、反応釜に入れた。この反応釜の中に上記モノマー混合液を更に入れ、2~4時間攪拌することで、モノマー混合液の液滴が所定の粒子径になるように、粒子径を調整した。この後85℃の窒素雰囲気下で9時間反応を行い、スペーサCを得た。得られたスペーサC熱水にて数回洗浄した後、分級操作を行った。得られたスペーサCでは、平均粒子径は20.1μm、粒子径のCV値は3.2%であった。
(シリコーン接着剤の調製)
1成分加熱硬化型シリコーン接着剤 TSE322(モメンティブパフォーマンスマテリアルズ社製)に対して、得られる接着剤中での含有量が2重量%になるようにギャップ制御粒子としてスペーサ1を添加し、遊星式攪拌機にて攪拌し、均一に分散させて、シリコーン接着剤を調製した。
上記シリコーン接着剤をシリンジに充填し、ディスペンサを用いてプリント基板上に厚さが20μmとなるように塗布した後、塗布した接着剤上に圧力センサチップを配し、150℃で10分加熱して硬化、接着し、圧力センサ構造体を得た。
シリコーン接着剤の調製の際、スペーサ2をスペーサ1の代わりに用いたこと以外は実施例1と同様にして、圧力センサ構造体を得た。
シリコーン接着剤の調製の際、スペーサ3をスペーサ1の代わりに用いたこと以外は実施例1と同様にして、圧力センサ構造体を得た。
シリコーン接着剤の調製の際、スペーサAをスペーサ1の代わりに用いたこと以外は実施例1と同様にして、圧力センサ構造体を得た。
シリコーン接着剤の調製の際、スペーサBをスペーサ1の代わりに用いたこと以外は実施例1と同様にして、圧力センサ構造体を得た。
シリコーン接着剤の調製の際、スペーサCをスペーサ1の代わりに用いたこと以外は実施例1と同様にして、圧力センサ構造体を得た。
(1)10%圧縮弾性率
フィッシャー社製「フィッシャースコープH-100」を用いて、上述した方法で、スペーサの10%圧縮弾性率を測定した。
スペーサを走査型電子顕微鏡で観察し、観察された画像における任意に選択した50個の各スペーサの最大粒子径を算術平均することにより求めた。
フィッシャー社製「フィッシャースコープH-100」を用いて、上述した方法で、スペーサの圧縮回復率を測定した。
フィッシャー社製「フィッシャースコープH-100」を用いて、スペーサを150℃、大気中で1000時間加熱した後の10%圧縮弾性率を測定した。スペーサの熱経時変化を以下の基準で判定した。
○:加熱後の10%圧縮弾性率の加熱前の10%圧縮弾性率に対する比が、0.95以上、1.05以下
△:加熱後の10%圧縮弾性率の加熱前の10%圧縮弾性率に対する比が、0.9以上、0.95未満、又は、1.05より大きく、1.10以下
×:加熱後の10%圧縮弾性率の加熱前の10%圧縮弾性率に対する比が、0.9未満、又は、1.10より大きい
得られた圧力センサ構造体の260℃でのシェア強度を測定した。シェア強度から、耐熱性:接続強度を判定した。
○○:シェア強度が150N/cm2以上
○:シェア強度が100N/cm2以上、150N/cm2未満
×:シェア強度が100N/cm2未満
得られた圧力センサ構造体を用いて、液槽式熱衝撃試験機(ESPEC社製「TSB-51」)を用いて、-40℃で5分間保持した後、120℃まで昇温し、120℃で5分間保持した後-40℃まで降温する過程を1サイクルとする冷熱サイクル試験を実施した。500サイクル後にサンプルを取り出した。
○○:接着層にクラックが生じておらず、かつ接着層が基板から剥離していない
○:接着層にわずかなクラックが生じているか、又は接着層が基板からわずかに剥離している
×:接着層に大きなクラックが生じているか、又は接着層が基板から大きく剥離している
2…スペーサ
3…第1の部材
4…第2の部材(半導体センサチップ)
5…接着層
Claims (6)
- 半導体センサチップの実装に用いられる接着剤であって、
シリコーン樹脂と、スペーサとを含み、
前記スペーサの10%圧縮弾性率が、10N/mm2以上、2000N/mm2以下であり、
前記スペーサの圧縮回復率が、20%以下であり、
前記スペーサの平均粒子径が、10μm以上、200μm以下である、半導体センサチップ実装用接着剤。 - 前記スペーサを150℃で1000時間加熱したときに、加熱後のスペーサの10%圧縮弾性率の加熱前のスペーサの10%圧縮弾性率に対する比が、0.95以上、1.05以下である、請求項1に記載の半導体センサチップ実装用接着剤。
- 前記接着剤中に含まれる前記スペーサにおいて、前記スペーサの平均粒子径に対して、平均粒子径が1.5倍以上であるスペーサが存在しないか、又は、前記スペーサの全個数100%中、前記スペーサの平均粒子径に対して、平均粒子径が1.5倍以上であるスペーサが0.1%以下の個数で存在する、請求項1又は2に記載の半導体センサチップ実装用接着剤。
- 前記スペーサが、シリコーンスペーサである、請求項1~3のいずれか1項に記載の半導体センサチップ実装用接着剤。
- 前記スペーサが、イソボルニル基を有する(メタ)アクリル化合物の重合体である、請求項1~3のいずれか1項に記載の半導体センサチップ実装用接着剤。
- 第1の部材と、
第2の部材である半導体センサチップと、
前記第1の部材と前記第2の部材とを接着している接着層とを備え、
前記接着層が、請求項1~5のいずれか1項に記載の半導体センサチップ実装用接着剤の硬化物である、半導体センサ。
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2017
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Cited By (2)
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KR20210015805A (ko) * | 2018-05-31 | 2021-02-10 | 세키스이가가쿠 고교가부시키가이샤 | 스페이서 입자, 접착제 및 접착 구조체 |
KR102599329B1 (ko) | 2018-05-31 | 2023-11-07 | 세키스이가가쿠 고교가부시키가이샤 | 스페이서 입자, 접착제 및 접착 구조체 |
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JP6322337B2 (ja) | 2018-05-09 |
EP3428600A4 (en) | 2019-09-25 |
EP3428600A1 (en) | 2019-01-16 |
JP2018142709A (ja) | 2018-09-13 |
JP6322336B2 (ja) | 2018-05-09 |
US10679925B2 (en) | 2020-06-09 |
KR102356926B1 (ko) | 2022-01-28 |
JP6971192B2 (ja) | 2021-11-24 |
EP3428599A1 (en) | 2019-01-16 |
US20190078002A1 (en) | 2019-03-14 |
KR20220019061A (ko) | 2022-02-15 |
CN108139286A (zh) | 2018-06-08 |
KR102331523B1 (ko) | 2021-11-26 |
EP3428600B1 (en) | 2023-05-24 |
CN108139286B (zh) | 2021-06-25 |
JPWO2017155117A1 (ja) | 2018-03-15 |
JPWO2017155116A1 (ja) | 2018-03-15 |
WO2017155116A1 (ja) | 2017-09-14 |
CN108139285B (zh) | 2021-06-04 |
KR20180117589A (ko) | 2018-10-29 |
US20190088573A1 (en) | 2019-03-21 |
KR20180118102A (ko) | 2018-10-30 |
US10790217B2 (en) | 2020-09-29 |
TWI751142B (zh) | 2022-01-01 |
EP3428599B1 (en) | 2023-06-07 |
EP3428599A4 (en) | 2019-09-25 |
TW201800545A (zh) | 2018-01-01 |
JP2018135525A (ja) | 2018-08-30 |
CN108139285A (zh) | 2018-06-08 |
TWI725131B (zh) | 2021-04-21 |
TW201800546A (zh) | 2018-01-01 |
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