JP6884458B2 - 硬化性オルガノポリシロキサン組成物および半導体装置 - Google Patents
硬化性オルガノポリシロキサン組成物および半導体装置 Download PDFInfo
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- JP6884458B2 JP6884458B2 JP2019501179A JP2019501179A JP6884458B2 JP 6884458 B2 JP6884458 B2 JP 6884458B2 JP 2019501179 A JP2019501179 A JP 2019501179A JP 2019501179 A JP2019501179 A JP 2019501179A JP 6884458 B2 JP6884458 B2 JP 6884458B2
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- organopolysiloxane
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- 239000000203 mixture Substances 0.000 title claims description 66
- 239000004065 semiconductor Substances 0.000 title claims description 41
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 33
- 229910004283 SiO 4 Inorganic materials 0.000 claims description 26
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 24
- 229910052710 silicon Inorganic materials 0.000 claims description 21
- 125000003342 alkenyl group Chemical group 0.000 claims description 20
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 18
- 239000010703 silicon Substances 0.000 claims description 18
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- 238000006459 hydrosilylation reaction Methods 0.000 claims description 11
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- 229910021485 fumed silica Inorganic materials 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 239000002683 reaction inhibitor Substances 0.000 claims description 3
- 239000007809 chemical reaction catalyst Substances 0.000 claims description 2
- 239000000047 product Substances 0.000 description 37
- -1 heptenyl group Chemical group 0.000 description 20
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- 125000003710 aryl alkyl group Chemical group 0.000 description 3
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- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 2
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Images
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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/12—Polysiloxanes containing silicon bound to hydrogen
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/52—Encapsulations
- H01L33/56—Materials, e.g. epoxy or silicone resin
-
- 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
- C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
- C09J183/04—Polysiloxanes
-
- 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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/06—Preparatory processes
- C08G77/08—Preparatory processes characterised by the catalysts used
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- C—CHEMISTRY; METALLURGY
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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Description
(A)一分子中に少なくとも2個のアルケニル基を有するオルガノポリシロキサン、
(B)平均単位式:
(R1 3SiO1/2)a(R1 2SiO2/2)b(R2SiO3/2)c(SiO4/2)d
(式中、R1は同じか又は異なる、脂肪族不飽和炭素結合を有さない一価炭化水素基もしくは水素原子であり、但し、一分子中、少なくとも2個のR1は水素原子であり、R2は脂肪族不飽和結合を有さない一価炭化水素基であり、a、b、cはそれぞれ、0<a<1、0<b<1、0≦c<0.2、0<d<1、但し、0.6≦a/d≦1.5、1.5≦b/d≦3、かつa+b+c+d=1を満たす数である。)
で表されるオルガノポリシロキサンレジン{(A)成分中のアルケニル基に対する(B)成分中のケイ素原子結合水素原子のモル比が0.5〜5となる量}、
および
(C)ヒドロシリル化反応用触媒(本組成物を硬化させるのに十分な量)
から少なくともなる。
R3R4 2SiO(R4 2SiO)m(R4HSiO)nSiR4 2R3
(式中、R3は同じか又は異なる、脂肪族不飽和炭素結合を有さない一価炭化水素基もしくは水素原子であり、R4は同じか又は異なる、脂肪族不飽和炭素結合を有さない一価炭化水素基であり、mは0〜50の数、nは0〜50の数であり、但し、nが0であるとき、R3は水素原子である。)
で表されるオルガノポリシロキサンを、(A)成分中のアルケニル基に対して(G)成分中のケイ素原子結合水素原子のモル比が多くとも0.3となる量含有してもよい。
(R5 3SiO1/2)e(R5 2SiO2/2)f(R5SiO3/2)g(SiO4/2)h(HO1/2)i
で表される。
(ViMe2SiO1/2)0.012(Me2SiO2/2)0.988
(ViMe2SiO1/2)0.007(Me2SiO2/2)0.993
(Me3SiO1/2)0.007(Me2SiO2/2)0.983(MeViSiO2/2)0.010
(Me3SiO1/2)0.01(MeViSiO1/2)0.01(Me2SiO2/2)0.96(MeSiO3/2)0.02
(ViMe2SiO1/2)0.005(Me2SiO2/2)0.895(MePhSiO2/2)0.100
(MeViSiO2/2)3
(MeViSiO2/2)4
(MeViSiO2/2)5
(R5 3SiO1/2)j(R5 2SiO2/2)k(R5SiO3/2)l(SiO4/2)p(HO1/2)q
で表される。
(ViMe2SiO1/2)0.10(Me3SiO1/2)0.33(SiO4/2)0.57(HO1/2)0.03
(ViMe2SiO1/2)0.13(Me3SiO1/2)0.35(SiO4/2)0.52(HO1/2)0.02
(ViMePhSiO1/2)0.10(Me3SiO1/2)0.45(SiO4/2)0.45(HO1/2)0.03
(ViMe2SiO1/2)0.09(Me3SiO1/2)0.31(SiO4/2)0.60(HO1/2)0.04
(ViMe2SiO1/2)0.10(Me3SiO1/2)0.40(SiO4/2)0.50(HO1/2)0.03
(R1 3SiO1/2)a(R1 2SiO2/2)b(R2SiO3/2)c(SiO4/2)d
で表されるオルガノポリシロキサンレジンである。
(Me3SiO1/2)0.23(MeHSiO2/2)0.51(SiO4/2)0.26
で表されるオルガノポリシロキサン、平均単位式:
(Me3SiO1/2)0.24(MeHSiO2/2)0.49(SiO4/2)0.27
で表されるオルガノポリシロキサン、平均単位式:
(Me3SiO1/2)0.24(Me2SiO2/2)0.10(MeHSiO2/2)0.40(SiO4/2)0.26
で表されるオルガノポリシロキサンが例示される。
R3R4 2SiO(R4 2SiO)m(R4HSiO)nSiR4 2R3
で表されるオルガノポリシロキサンが例示される。
Me3SiO(MeHSiO)10SiMe3
HMe2SiO(Me2SiO)10SiMe2H
Me3SiO(MeHSiO)80SiMe3
Me3SiO(Me2SiO)30(MeHSiO)30SiMe3
Me2PhSiO(MeHSiO)35SiMe2Ph
本発明の半導体装置は、筺体内の半導体素子が上記組成物からなる接着剤の硬化物により接着されていることを特徴とする。この半導体素子としては、具体的には、発光ダイオード(LED)、半導体レーザ、フォトダイオード、フォトトランジスタ、固体撮像、フォトカプラー用発光体と受光体が例示され、特に、発光ダイオード(LED)であることが好ましい。
(Me2ViSiO1/2)0.042(Me2SiO2/2)0.958
で表される、粘度60mPa・sのオルガノポリシロキサン(ビニル基の含有量=1.53質量%)
(a−2)成分:平均単位式:
(Me2ViSiO1/2)0.012(Me2SiO2/2)0.988
で表される、粘度550mPa・sのオルガノポリシロキサン(ビニル基の含有量=0.45質量%)
(a−3)成分:平均式:
(MeViSiO)4
で表される、粘度4mPa・sの環状メチルビニルポリシロキサン(ビニル基の含有量=30質量%)
(a−4)成分:平均式:
HO(MeViSiO)20H
で表される、粘度30mPa・sのメチルビニルポリシロキサン(ビニル基の含有量=30質量%)
(a−5)成分:平均単位式:
(Me2ViSiO1/2)0.55(Me3SiO1/2)0.05(SiO4/2)0.40
で表される、室温で固体のオルガノポリシロキサン(ビニル基の含有量=19.0質量%)
(a−6)成分:平均単位式:
(Me2ViSiO1/2)0.09(Me3SiO1/2)0.43(SiO4/2)0.48(HO1/2)0.03
で表される、室温で固体のオルガノポリシロキサン(ビニル基の含有量=3.0質量%)
(a−7)成分:平均単位式:
(Me2ViSiO1/2)0.10(Me3SiO1/2)0.45(SiO4/2)0.45(HO1/2)0.02
で表される、室温で固体のオルガノポリシロキサン(ビニル基の含有量=3.0質量%)
(Me3SiO1/2)0.23(MeHSiO2/2)0.51(SiO4/2)0.26
で表されるオルガノポリシロサキン(重量平均分子量=18000、ケイ素原子結合水素原子の含有量=0.78質量%)
(b−2)成分:粘度が510mPa・sであり、平均単位式:
(Me3SiO1/2)0.24(MeHSiO2/2)0.49(SiO4/2)0.27
で表されるオルガノポリシロサキン(重量平均分子量=16300、ケイ素原子結合水素原子の含有量=0.75質量%)
(b−3)成分:粘度が640mPa・sであり、平均単位式:
(Me3SiO1/2)0.24(Me2SiO2/2)0.10(MeHSiO2/2)0.40(SiO4/2)0.26
で表されるオルガノポリシロサキン(重量平均分子量=15400、ケイ素原子結合水素原子の含有量=0.78質量%)
(b−4)成分:粘度が230mPa・sであり、平均単位式:
(HMe2SiO1/2)0.51(Me2SiO2/2)0.15(SiO4/2)0.34(HO1/2)0.03
で表されるオルガノポリシロサキン(重量平均分子量=2100、ケイ素原子結合水素原子の含有量=0.80質量%)
(b−5)成分:粘度が120mPa・sであり、平均単位式:
(HMe2SiO1/2)0.67(SiO4/2)0.33
で表されるオルガノポリシロキサン(重量平均分子量=1310、ケイ素原子結合水素原子の含有量=0.95質量%)
(b−6)成分:粘度が10mPa・sであり、平均式:
Me3SiO(MeHSiO)10SiMe3
で表されるオルガノポリシロキサン(重量平均分子量=8800、ケイ素原子結合水素原子の含有量=1.6質量%)
(d)成分:BET比表面積が115〜165m2/gであり、その表面がヘキサメチルジシラザンで疎水化処理されたフュームドシリカ(日本アエロジル社製の商品名:RX200)
(e)成分:1−エチニルシクロヘキサン−1−オール
(f)成分:25℃における粘度が30mPa・sである分子鎖両末端シラノール基封鎖メチルビニルシロキサンオリゴマーと3−グリシドキシプロピルトリメトキシシランの縮合反応物
硬化性オルガノポリシロキサン組成物を150℃で1時間プレス成形することによりシート状硬化物を作製した。このシート状硬化物の硬さをJIS K 6253に規定されるタイプDデュロメータにより測定した。
25mm×75mmの銀めっきした鋼板上に、硬化性オルガノポリシロキサン組成物をディスペンサーにより約300mgづつを5ヶ所に塗布した。次に、この組成物に厚さ1mmの10mm角のガラス製チップを被せ、1kgの板により圧着した状態で、150℃で2時間加熱して硬化させた。その後、室温に冷却し、シェア強度測定装置(西進商事株式会社製のボンドテスターSS−100KP)によりダイシェア強度を測定した。
前記方法により作製したダイシェア試験片内の気泡の数を目視により数えた。
表1に示した混合比で硬化性オルガノポリシロキサン組成物を調製した。硬化物の諸特性を上記のようにして測定し、それらの結果を表1に示した。
2 インナーリード
3 ダイパッド
4 接着材
5 発光ダイオード(LED)チップ
6 ボンディングワイヤ
7 封止材
Claims (8)
- (A)一分子中に少なくとも2個のアルケニル基を有するオルガノポリシロキサン、
(B)平均単位式:
(R 2 3SiO1/2)a(R1 2SiO2/2)b(R2SiO3/2)c(SiO4/2)d
(式中、R1は同じか又は異なる、脂肪族不飽和炭素結合を有さない一価炭化水素基もしくは水素原子であり、但し、一分子中、少なくとも2個のR1は水素原子であり、R2は脂肪族不飽和結合を有さない一価炭化水素基であり、a、b、c、及びdはそれぞれ、0<a<1、0<b<1、0≦c<0.2、0<d<1、但し、0.6≦a/d≦1.5、1.5≦b/d≦3、かつa+b+c+d=1を満たす数である。)
で表される、8,000以上の重量平均分子量(Mw)を有するオルガノポリシロキサンレジン
{(A)成分中のアルケニル基に対する(B)成分中のケイ素原子結合水素原子のモル比が0.5〜5となる量}、
および
(C)ヒドロシリル化反応用触媒(本組成物を硬化させるのに十分な量)
から少なくともなる硬化性オルガノポリシロキサン組成物。 - さらに、(D)BET比表面積が20〜200m2/gであるフュームドシリカを、(A)〜(C)成分の合計100質量部に対して1〜20質量部含有する、請求項1に記載の硬化性オルガノポリシロキサン組成物。
- さらに、(E)ヒドロシリル化反応抑制剤を、(A)〜(C)成分の合計100質量部に対して0.001〜5質量部含有する、請求項1または請求項2に記載の硬化性オルガノポリシロキサン組成物。
- さらに、(F)接着促進剤を、(A)〜(C)成分の合計100質量部に対して0.01〜10質量部含有する、請求項1乃至3のいずれか1項に記載の硬化性オルガノポリシロキサン組成物。
- さらに、(G)平均式:
R3R4 2SiO(R4 2SiO)m(R4HSiO)nSiR4 2R3
(式中、R3は同じか又は異なる、脂肪族不飽和炭素結合を有さない一価炭化水素基もしくは水素原子であり、R4は同じか又は異なる、脂肪族不飽和炭素結合を有さない一価炭化水素基であり、mは0〜50の数、nは0〜50の数であり、但し、nが0であるとき、R3は水素原子である。)
で表されるオルガノポリシロキサンを、(A)成分中のアルケニル基に対して(G)成分中のケイ素原子結合水素原子のモル比が多くとも0.5となる量含有する、請求項1乃至4のいずれか1項に記載の硬化性オルガノポリシロキサン組成物。 - 硬化して、JIS K 6253に規定されるタイプDデュロメータ硬さが30〜70である硬化物を形成する、請求項1乃至5のいずれか1項に記載の硬化性オルガノポリシロキサン組成物。
- 半導体素子の接着剤である、請求項1乃至6のいずれか1項に記載の硬化性オルガノポリシロキサン組成物。
- 半導体素子が請求項1乃至6のいずれか1項に記載の硬化性オルガノポリシロキサン組成物の硬化物により接着されていることを特徴とする半導体装置。
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